Section A - Collaborative Research Project (CRP) State of the art, aims and objectives The process of self-assembly of large functional molecules on surfaces is the single most important step in creating thin films of complex organic molecules for a number of applications in molecular sensing, enantioselective catalysis and recognition structures, and in the rapidly developing fields of molecular devices, such as optoelectronic and logic circuits [1]. In order to use molecular layers in laterally structured arrangements, i.e. in device applications, the control of supramolecular self-organisation on surfaces is of central importance. To this aim, it is important to combine the ability to synthesise molecules and fabricate templates and substrates with a detailed understanding of the balance between intermolecular forces and molecule-substrate interactions. This may be achieved using powerful surface sensitive techniques, such as electron spectroscopies (photoemission, absorption) and scanning tunnelling microscopy (STM). Indeed, a considerable effort is currently being devoted to the microscopic description of molecule/surface conformation, bonding and electronic states in individual (functionalised) molecules and supramolecular networks [2]. However, most of these studies have focused on planar metallic or semiconducting surfaces, and very little work is done using functionalised substrates and templates [3]. The latter are not only useful to tune particular network geometries and properties, but are indeed required for a massive, parallel supramolecular selfassembly in technological applications and devices. Supramolecular self-organisation is driven by long-range dipolar interactions and short-range ionic or hydrogen bonding between molecules. Within the limits of growth kinetics, the resulting network depends on the general properties of the molecule and the details of the functional groups, although particular configurations may be induced by the electronic structure of the surface [4], or forced by the morphology in a templated substrate [3]. The latter is the case of vicinal surfaces with one-dimensional arrays of steps, which are natural templates to self-assemble one-dimensional molecular structures attached to surface steps [5]. Such one-dimensional assemblies are the simplest supramolecular networks, and hence ideal to investigate molecule-molecule and substrate-molecule interactions, supramolecular growth kinetics, as well as the physical and chemical properties of the resulting one-dimensional molecular arrays. Vicinal surfaces are easily obtained by a macroscopic tilt or miscut (1º to 15º) with respect to a high-symmetry surface, resulting in one-dimensional step superlattices on the nanometer scale. Using noble metal surfaces as model systems, Ortega’s, Michel’s and Greber’s groups have pioneered the work on the basic description of the electronic states of vicinal surfaces within the last few years [6]. Noble metal vicinal surfaces are found to exhibit complex reconstructions and varying electronic properties as a function of miscut and step type, which can thus become tuning parameters to tailor one-dimensional supramolecular assemblies. The on-going “MOLVIC” Collaborative Research Project (CRP) aimes at characterising and systematically testing such noble metal vicinal surfaces as one-dimensional templates for supramolecular assembly. It is focused on fundamental aspects, such as the structural stability of the template upon molecule adsorption, the identification of ordered phases (arrays) and their geometric and electronic properties. Our approach encompasses a characterisation of individual molecule properties (conformation, electronic levels), and molecule-molecule as well as moleculesurface interactions within the assembly. We focus on a restricted number of molecules, in particular those which exhibit weak molecule-molecule and molecule-surface interactions, such as fullerenes, and pentacene, simple synthetic molecules likely to force linear hydrogen bonding (benzodiguanamine) and chiral molecule, such as D- and L-cysteine and tartaric acid. The knowledge acquired during the current CRP is a major step towards a true customisation of onedimensional molecular assemblies. The new CRP will expand towards a wide variety of molecules with a higher degree of functionalization: PMMA, diynes, aminoacids, phthalocyanines, functionalised and doped (“endo-“) fullerenes, and aromatic molecules with different symmetries and functional groups, such as PTCDI and NTCDI. Most of these will be specifically synthesised by the associated group in Toulouse [AP1] and the new partner in Kiel [IP5]. The new CRP will also incorporate sophisticated techniques for a more detailed electronic and crystallographic characterisation, namely SPALEED [IP3], photoelectron diffraction and timeand spin-resolved photoemission [IP6], circular dichroism in absorption and photoemission [IP4], and a combination of laser illumination and photoelectron spectroscopy, in order to address molecular switching processes in adsorbed layers [IP4]. Hydrogen bonding in supramolecular chemistry will be investigated by using aromatic molecules, synthesised by Gourdon, with linear symmetry and varied end groups. We will test one-dimensional supramolecular assembly via homogeneous symmetric bonding, e.g, using di-imide or di-amine-like molecules [7,IP1], asymmetric bonding introducing asymmetric end groups, e.g, pyrazole-carboxylic-like molecules [IP1]. Moreover, we will coadsorb molecules for heterogeneous bonding, e.g, mixing amine and imine groups [8]. Ionic and dipole-like molecule/molecule and substrate/molecule bonding can be explored with molecular chains of fullerenes and endofullerenes. Functionalized fullerenes, such as PCBA will likely introduce molecule/molecule hydrogen bonding and strong changes in molecule/surface interaction. Moreover, we intend to step towards the preparation of N@C60 spin-chains, where the spins of the isolated nitrogen atom are expected to order and are used to detect the magnetic properties of the environment [9, IP6]. On the other hand, based on the variety of ordered patterns achieved with C60 and C70 fullerenes on Au(111) vicinals [IP1,IP2], we will use such patterns as templates for “chemistry on the surface”. Herges will provide, on the one hand, retinal molecules with functional groups for appropriate surface attachment, which will be used to test light-induced isomerization of one-dimensional, self-assembled retinals (IP6), and on the other hand, appropriate molecules for linear polymerization of polyacetylenes and proteins. Diynes can be polymerised to form polyacetylenes which are semiconducting molecular wires consisting of a single C-C backbone. Their conductivity depends on the substitution and the environment which makes the material “designable” and interesting for molecular electronics. Oxazolidine-2,5-diones, malonic acid monoazides and -isocyanato carboxylic esters form proteins if heated, irradiated, initiated by amines. The preparation of isolated, linear stretched protein chains on a surface so far has not been achieved, and might contribute to answering fundamental questions in protein folding. Oxazolidine-2,5-dione crystals are known to polymerise in a chain reaction once initiated nucleophilic attack, and malonic acid monazides react by photochemical initiation. It might be possible to initiate the polymerisation using the STM tip and control the formation of the protein chain. In order to access the full range of system interactions, molecular assemblies above and below the supramolecular level will be explored. Weak molecule-molecule interactions, such as dipole- or substratemediated, characterize dilute phases, but also dense aromatic hydrocarbon layers, such as pentacene, where the hydrogen bond is not formed. The latter are particularly sensitive to surface state-mediated interactions [4], and hence vicinal surfaces with tunable electronic properties may be ideal to tailor the growth of ordered adlayers. Au vicinal surfaces are ideal for testing the full range of system interactions due to the presence of reconstructed patterns that force coverage-dependent ordered phases in the 5-10 nm range. These in turn can be studied with reciprocal space techniques, such as angle resolved PES, SPALEED and surface X-ray diffraction [IP3]. However, due to the inherent complexity, with large unit cells and weak molecule-molecule interactions we will combine high resolution structural and spectroscopic capabilities in the same Lab system, such as PES and SPALEED [IP3], PES and STM [IP1,IP2]. Different kinds of interactions, other than the one mediated by surface electronic states, are to be explored [IP1,IP3,IP4], such as the formation of an adsorption-induced strain superlattice [10], which may also modify the surface electronic structure [11]. Besides the -conjugated molecules, dilute phases of C60, C70 fullerenes and endofullerenes (N,K,Na) on a variety of vicinal surfaces will be investigated [IP1,IP6]. Beyond weak hydrogen or ionic bonding, the strong covalent molecule-molecule interaction will be tested in polymerised chains [IP2]. There is an enormous interest in this kind of system, since one-dimensional bands and hence, one-dimensional electron conduction is expected. In this CRP vicinals will be used as templates for molecules which can be polymerised. We will test the formation of insulating wires of PMMA and conducting 1D assemblies of diynes and amino acids, taking advantage of the step dipole moment. Polymerisation will be induced either with electrons (holes) from the STM tip or by illumination. Strategy and work plan (for details see individual work-plans) As a general scientific strategy, we aim at determining the hierarchy of forces that drive supramolecular selfassembly, by a detailed analysis of the structural and the electronic properties in a number of different cases. The current CRP is aimed at providing the electronic and structural characterisation for a wide variety of noble metal vicinal surfaces and templates, and a selective group of molecular assemblies. We have already acquired a remarkable control and knowledge of the general substrate properties [5], necessary to assess the role of the substrate in determining both the substrate/molecule interaction, and the morphology of assemblies with molecules of higher functionalisation. The extended CRP will focus on the full range of molecule/molecule interactions and hence varied molecular functionalisations will be tested. For aromatic chains with hydrogen bonding, we define a double strategy, i.e. varying the chemical nature of the end groups (diaminotriazine, imide), and the strength of the bonding by combining molecules or by asymmetric functionalisation [7,8]. For C60 and C70 fullerenes the whole range of interactions can be tuned by functionalisation (hydrogen bonding, polar groups), external doping (ionic, dipolar, magnetic), and polimerisation. The covalent bonding will be intensively investigated in one-dimensional chains of aminoacids, proteins and dyines. Such a thorough and complex approach requires a strong collaborative research, and a continuous exchange of personnel, materials and information among the different groups. Moreover, collaborative experiments using European synchrotron radiation facilities naturally forces parallel, coordinated work at home labs. The overall CRP strategy is sketched below. Every box contains the characteristic strengths and research to be carried out at home Labs in each group: types of molecules to be synthesised or searched, the distinct technique to be used, and the specific issues. At this level, the CRP work is necessary, since exchange of substrates and molecules (green and black lines, respectively) is needed. Small boxes define a direct collaborative research, namely, electronic/structural characterisation through photon/electron spectroscopies at European syncrotrons (BESSY, SLS, Elettra, ESRF), as well as joint home lab experiments with exchange of personnel (Kiel, Berlin, San Sebastian). From this Figure, the European added value of the CRP is evident. 1.- Supramolecular self-organisation of aromatic molecules: AP1(synthesis) a) Lab Work: IP1(STM+ARPES), IP3 (SPALEED, ARPES, SXRD), IP4 (XRCD for chirality). b) Lab Collaboration: IP1+IP2, using 4K-STM (molecule conformation) and HR-ARPES (ordered phases). c) Lab Collaboration IP3+IP4, using XRCD to study chirality d) Synchrotron Collaboration IP1+IP2+IP3+IP4+IP6 (absorption/photoelectron spectroscopy, XRCD) 2.- Supramolecular self-assembly of fullerenes: a) Lab work: IP6 (XPD, spin-resolved, time-resolved PES for fullerenes and magnetic endofullerenes), IP1 (STM+ARPES for dilute phases and functionalised fullerenes by IP5) b) Synchrotron Collaboration IP1+IP2+IP6 (photoelectron spectroscopy, XRCD). 3.- Polymerisation: Lab collaboration: IP2+IP5 (Synthesis, light induced and tip-induced polymerisation, 4K-STM) 4.- Light-induced isomerization: Lab and synchrotron collaboration: IP4+IP5+IP6 (synthesis, light induced isomerization, XRCD,XPD). Bibliography: [1] "Molecular Electronics: Science and Technology”, eds. A. Aviram and M. Ratner, Annals of the New York Academy of Sci. vol. 852, New York 1998; Heath et al., Science 280, 1716 (1998); Chen et al., Science 286, 1550 (1999); Collier et al., Science 289, 1172 (2000); see also the special issue Science 295, 2395-2421 (2002). [2] S. M. Barlow and R. Raval Surf. Sci. Rep. 50, 201 (2003); F. Rosei et al., Prog. Surf. Sci. 71, 95 (2003); V. Humblot et al., Prog. Surf. Sci. 76, 1 (2004). [3] J. N. Crain et al., J. Appl. Phys. 90, 3291 (2001); R. Otero et al. Angewandte Chemie, International Edition 43, 2092 (2004) and Nature Materials 3, 779–782 (2004). [4] S. Lukas et al., Phys. Rev. Lett. 88, 028301 (2002); J. Repp et al, Phys. Rev. Lett. 85, 2981 (2000); E. C. H. Sykes et al., J. Am. Chem. Soc. 127, 7255 (2005). [5] See Annual report of the on-going “MOL-VIC” CRP. [6] Ortega: J. Phys. Cond. Mat. 15, S3281 (2003), Phys. Rev. Lett. 84, 6110 (2000), Phys. Rev. Lett. 87, 107601 (2001), Phys. Rev. Lett 95, 066805 (2005); Greber: Phys. Rev. Lett. 88, 237601 (2002); 90, 177402 (2003); 92, 016803 (2004); 92, 196805 (2004); Michel: Phys. Rev. Lett. 93, 137602 (2004). [7] D. L. Keeling et al., Nanoletters 3, 9 (2003); D. Laliberté et al., J. Org. Chem. 69, 1776 (2004). [8] J. A. Theobald et al., Nature 424, 1029 (2003). [9] T. Almeida Murphy et. al., Phys. Rev. Lett. 77 (1996) 1075, W. Harneit, Phys. Rev. A 65 (2002) 032322. [10] C. Cohen et al, Surf. Sci. 490, 336 (2001). [11] D. Sekiba et al, Phys. Rev. Lett. 94, 0168081 (2005). Deliverables and milestones (referred to individual work-plans) End of the on-going CRP (2006): Fully characaterized vicinal surfaces and templates, characterization of molecular assemblies of planar (benzodiguanamine, PTCDI, NTCDI) molecules with hydrogen-bonding, fullerenes with ionic interactions, and pentacene (substrate mediated interactions) on some vicinals. Chirality on cysteine. General CRP workshop and kick-off meeting 1st year: New equipment set-up and testing. Synthesis of new molecules from IP5 and AP1. First experiments for the structural characterization of one-dimensional assemblies of aromatics with symmetric and asymmetric bonding (IP1, IP3, IP4) , functionalized fullerenes and endofullerenes (IP1,IP6) and their polimerisation (IP2). 2nd and 3rd year: Full characterization of supramolecular one-dimensioanl assemblies of aromatics (AP1, IP1, IP3, IP4) and functionalized fullerenes and endofullerenes (IP1,IP6), light isomerization (IP4, IP6) and chain polimerisation (IP2,IP5). Overall budget of the CRP BUDGET ITEMS EUROCORES Funding Agency (EFA) Estimate of Funding PI 1 Ortega Ministerio de Educación y Ciencia (Spain) (in Euros) Salary costs Ph.D. student(s) Post-doc. Researcher(s) Senior researcher (s) Technician(s) Estimate of Funding PI 2 Berndt Deutsche Forshungsgemeinshaft (Germany) (in Euros) Estimate of Funding PI 3 Michel Ministerio de Educación y Ciencia (Spain) (in Euros) 3 x 56000 = 168000 2x35360=70720 Estimate of Funding PI 4 Horn Deutsche Forshungsgemeinshaft (Germany)) (in Euros) Estimate of Funding PI 5 Herges Deutsche Forshungsgemeinshaft (Germany)) (in Euros) 3 x 56000 = 168000 3 x 48000 = 144000 Estimate of Funding PI 6 Greber Swiss National Science Foundation (Switzerland) (in Euros) Estimate of TOTAL Funding (in Euros) 238753 789473 Guest Prof: 20000 32246 20000 32246 Equipment per item item 1 UV source + optics 19700 item 2 item 3 Item 4 Item 5 Travel conferences, worksh.,visits Consumables / Runn. Costs Including analysis costs Publication, Dissem. Cost Overheads if applicable Electron analyzer 133400 Quad. mass spectrom. 12000 UHV chamb. and gaug. 20000 Ion, turbo and rotary pumps, gate valves 20000 High Intens. Light sourc., fiber optic lamp 21000 Evaporator comp. 6000 HPLC software 8000 245100 Transfer rod: 5000 12000 12000 6000 14000 6300 50300 12000 15000 6000 32000 93000 2000 0 Channeltrons 5000 23 000 3000 19% 26927 0 20% 66860 19% 29906 5000 123693 Others Travel to synchrcotron 3000 187306 T O T A L 214700 171647 168000 0 administrative coordin. 2000 219000 403159 5000 1363812 Description of the Collaboration: SCIENTIFIC TRACK RECORD The project is structured as an interdisciplinary effort aimed at understanding supramolecular assembly through a combination of preparation and analysis techniques. The collaborating groups contribute and share their know-how in vicinal surface preparation and chemical synthesis, state-of-the-art experimental techniques, and a considerable experience in materials science and surface/interface research. The current, on-going CRP combines the expertise of the groups in nanostructured template preparation (Ortega, Michel), molecule synthesis (Gourdon), single molecule manipulation and spectroscopy (Berndt) and electronic structure characterisation (Horn, Ortega, Michel), and theory (Joachim). The new CRP will be strengthened by two new groups: strong synthetic chemistry capabilities (Herges), and one of the leading groups worldwide for surface structural characterisation and analysis (Greber). The combination of expertise in the new team will make it possible to expand the CRP research to new classes of molecular systems, and novel aspects such as molecular magnetism, molecular chirality, and electron dynamics. Theoretical support will be provided by prestigious groups out of the CRP (see IP1.B4 and IP2.B4). Ortega has devoted most of his research career to the field of electronic states in nanostructures. Related to this project, during the recent six years, Ortega, together with Michel and Greber, has paved the way on the fundamental understanding of electronic states in vicinal surfaces using angle resolved photoemission. This is demonstrated by the large number of high profile papers (8 PRL’s) published by these authors on the subject (see CV’s). The search performed by Ortega currently extends to a variety of one-dimensional structures with tailored electronic properties: from step and facet arrays in noble metal surfaces to adsorption-induced atom chain structures and stripes. As a side effect of this broad research, Ortega posseses a large collection of about 30 different vicinal single crystal surfaces (Au,Cu,Ag,Si,Ge) which are at the disposal of the other CRP members. Using some of these surfaces, Ortega’s group is currently carrying out individual STM as well as collaborative spectroscopy/STM experiments with Berndt, Michel and Horn on self-assembly of aromatic molecules (synthesized by Gourdon) and fullerenes. Ortega’s group scientific quality output reflects in the 6 PRLs published since 2000. Berndt has an extensive experience in the field of low-temperature tunneling microscopy and spectroscopy. Among the different fields pursued in recent years, we must mention high-resolution spectroscopy of noble metal surface states, resulting in an accurate determination of lifetimes of surface state electrons. We were able of observing the Kondo effect over a single magnetic adatom and have demonstrated the modification of electronic structure of a single in atomic resonators fabricated by atom manipulation. Recently, we investigated STM-induced luminescence from quantum wells and studied transport to single atoms and molecules. A second focus of our work is tunneling microscopy of molecules. We have observed the self-assembly of supramolecular clusters and chains and have demonstrated the feasibility of separating a racemic mixture of chiral molecules into enantiomerically pure domains by molecular manipulation with the STM. Recently, we have studied the conformational changes of large molecules (lander, C90H98) upon adsorption in collaboration with the group in Toulouse. Since 2000 we have published 9 articles in Phys. Rev. Lett. (one in print), one in Nature, one in Science. The scientific activity of Michel has been devoted during the last ten years to the investigation of the structural and electronic properties of complex surface system, paying special attention to the role of the electronic energy in the stabilization of surface phases. To this end, different experimental techniques have been applied to characterize the properties of surfaces and interfaces, developing a true multitechnique approach to the problems. This includes surface x-ray diffraction, photoelectron diffraction, inelastic He atom scattering, and angle-resolved photoemission. This work has given rise to several important publications in the field (see list of most relevant papers). Since 1999, Michel, Ortega and Greber have worked in the analysis of vicinal metal surfaces. The current CRP has extended this work to the analysis of the self assembly of organic molecules on vicinal surfaces and has already obtained promising results. Electronic structure investigations are at the center of interest in the group of Horn. Low-dimensional systems such as metallic quantum wells on semiconductors, and terrace structures on clean surfaces on the one hand, and on the other hand, complex quasicrystalline alloy phases which exhibit perfect atomic order despite the absence of translational symmetry, have been studied using angle resolved photoemission as well as scanning tunneling microscopy and spectroscopy. This work has revealed general features of the electronic states in such systems, with relevance to a broad range of material systems. The group has recently used circular cichroism in core level photoemission to identify chiral centers in adsorbed molecules, an interesting subject in the context of this proposal. Focus of research of Herges is the synthesis of carbon rich materials and the design of photoswitchable compounds to construct molecular machines such as photochemically driven pincers, motors, ion pumps, and chemical synthesizers. The Herges group achieved the first rational synthesis of a short section of a carbon nanotube and the first synthesis of a Möbius annulene. The scientific record is documented by a number of publications in reputed journals (20 papers in Angew. Chem. one publication in Science and in Nature). Greber's research activity in the past five years has been generally focused on the interplay between electronic structure and morphology in low dimensional systems, using a multitechnique approach. Related to this CRP, it is of particular importance, on the one hand, his contributions in the field of novel, self-assembled nanostructures, such as boron nitride layers (e.g. nanomesh) and fullerene chains on vicinal surfaces. Furthermore the angle scanned photoelectron diffraction technique was applied to the determination of the absolute chirality of molecules. The quality of scientific output is reflected in the abundant number of high profile articles, e.g., six Phys.Rev.Letters and two Science in the past five years. The scientific activity of Gourdon during the past 7 years has been focused on the design, synthesis and structural studies of molecular devices for single molecule experiments by UHV STM and AFM. One of the key points has been the development of molecular landers, in which a rigid polyaromatic part is lifted above a metallic substrate by molecular spacers. It has allowed the first demonstration of molecular moulding, the measurement of contact conductance on a single molecule, the study of single molecule mechanics and switching etc.. EXPERTISE AND CONTRIBUTIONS EXPECTED FROM EACH GROUP TO THE CRP Ortega: Expertise on vicinal surface and template fabrication. Expertise on electronic structure analysis from stepped and facetted surfaces with angle-resolved photoemission. The expected contributions are: providing customised templates, characterising electronic properties of templates and molecular assemblies by combining STM and angle-resolved photoemission in the home Lab in San Sebastian, collaborating in synchrotron radiation experiments. Berndt: Expertise on atomic and molecular manipulation using low-temperature STM. 2D-chiral molecular structures. Determination of local electronic structure by tunnelling spectroscopy and photonemission STM. The expected contributions are: testing tailored templates for molecular self-organisation, characterising the assemblies and assessing local electronic structure. The low-temperature capabilities of the STM (operation at 5 and 50 K) allow to suppress mobility, which usually prevents tunnelling spectroscopy with sub-molecular spatial resolution at ambient or moderately low (150 K) temperatures. Michel: Expertise on vicinal surface and template fabrication. Expertise on electronic and structural analysis with core-level photoemission, angle-resolved photoemission, photoelectron diffraction, surface x-ray diffraction and x-ray standing waves. The expected contribution is the accurate characterisation of the structure and the electronic properties of templates and complex molecular assemblies with those techniques, using also synchrotron radiation laboratories. Horn: Expertise and contribution will cover the analysis of molecular adsorbate electronic structure, and adsorbate geometry using valence level photoemission, core level photoelectron diffraction, and x-ray absorption techniques. The use of circularly polarised x-rays will provide insight into the influence of the adsorption and assembly process on chiral centers of adsorbed layers. Herges: Expertise on synthesis of complex organic molecules and supramolecular structures, namely tube- and belt-like aromatic and Moebius aromatic compounds. The contribution to this project will be the synthesis and structural characterisation of functionalised fullerenes and related compounds suitable for the formation of onedimensional supramolecular structures on vicinal surfaces. Greber: Expertise on vicinal and chiral surfaces and formation of molecular arrays. Expertise on angle scanned X-ray Photoelectron diffraction (XPD), applied to molecular systems, with access to a state of the art experiment on a synchrotron light source. Full access to a surface science lab with XPS, LEED, STM, 2PPE, and Spin-Polarized Photoemission. Gourdon: Expertise on design and synthesis of molecules for nanosciences such as wires, switches, templates or mechanical molecular devices. The expected contribution is to provide specifically designed molecules for adsorption on various metallic templates. EUROPEAN ADDED VALUE The European added value of the CRP is strongly reflected in the variety of groups from different countries involved, and in the strong necessity of the collaborative research (see “Strategy and Workplan” in section A). There are good complementarities between the teams, showing that the collaborative project constitutes a coherent body, able to generate synergies. From the multitude of experimental approaches, the diversity of methods of analysis, and the acces to the different national facilities, it is clear that no similar research project could be undertaken at national level, indicating the need of a collaborative European project and the existence of a European added value from the collaboration. It is also remarkable that state of the art European Synchrotron Radiation Facilities (ESRF, BESSY, Elettra, SLS) are deeply involved in such collaborative research. Section B - Individual Projects (IP) IP1-B1 PI: Enrique Ortega, Universidad del País Vasco, San Sebastian One-dimensional self assembly of aromatic molecules and functionalized fullerenes 1.- Aims and Objectives The general objective of IP1 is studying one-dimensional supramolecular self-organization in a variety of molecule/vicinal surface systems, with the triple aim of: a) Identifying the underlying microscopic mechanisms that drive the self-assembly process, determining the kinetic limiting parameters and the specific role played by substrates, molecules and functional groups. b) Providing a thorough characterisation of structural and electronic properties of such one-dimensional supramolecular assemblies. c) As a result, defining the appropriate combinations of substrates, molecules, and functional groups, and the procedures to obtain one-dimensional supramolecular structures with desired properties. 2.- Methodology We will utilize a variety of molecule/surface systems trying to cover the widest possible range of molecule/molecule and substrate/molecule interactions. That will provide the necessary knowledge in order to to proceed with the refined selection of substrates, molecules and functional groups for a customized system. The experimental approach is based on a powerful combination of variable temperature Scanning Tunneling Microscopy and High-Resolution Angle Resolved Photoemission within the same experimental chamber. A more accurate study of individual molecule conformations will be carried out in collaboration with IP2 (4K STM), whereas synchrotron radiation studies (absorption, Photoemission) will be done in collaboration with IP2, IP3, IP4 and IP6 at the SLS, Elettra, and BESSY facilities. Initially we plan to work with a limited number of vicinal substrates and templates, and explore other substrates depending on the results obtained. The selected group comprise Au(111) vicinals with different electronic/structural properties (step arrays, facets and kinks) and Ag overlayers on Cu(111) vicinals. We will focus on two groups of molecules which, in principle, define two distinct types of interactions with the substrate, i.e., aromatic chains with functionalized end groups (pi-bonding to the surface) and fullerenes (ionic bonding). For aromatic molecules (synthesized by AP1) we fix the linear geometry and vary the chemical nature of the end groups (diaminotriazine, imide), and the strength of the intermolecular bonding by combining different molecules or by asymmetric end-group functionalisation (acid-N). For fullerenes we plan to introduce hydrogen bonding using molecules with functional acid (PCBA), and polar (INDAN, BINDAN, synthesized by IP5), and also tune the ionicity by external doping (with alkali metals, endofullerenes). Succesive experiments for each group of molecules will increase the degree of complexity, i.e., from the simplest linear, symmetric aromatic molecules and plain fullerenes on step arrays we will move towards coadsorbtion of molecules and endofullerenes and the use of complex Ag/Cu nanostructured templates. 2.- Work plan, milestones and deliverables 2.1.- Expected outcome of the ongoing CRP (end of 2006): a) Template characterization: The extensive work in surface/template fabrication and characterization will provide a variety of one-dimensional structures with well-characterized geometry, chemical composition and electronic properties. We will be able of selecting geometry and electronic properties in vicinal surfaces and templates by selecting surface and step type and density [1], as well as chemical contrast in two-phase striped structures [2]. Nonetheless, based on the stability of the substrate/template upon molecule adsorption, we are already defining a selective set of surfaces/templates for prospective experiments with molecules (see Figure 1). These comprise: i) Au(778), canonical example of an step array (36 Å periodicity) with a high degree of homogeneity over huge areas of the surface. Electronic states are quasi-one-dimensional minibands of electrons confined in terraces [1]. ii) Au(788), same as Au(778), but with a perpendicular, ordered fcc/hcp reconstruction pattern (70 Å periodicity) along terraces, thereby defining a square mesh. (Figure 1). i) Au(433), faceted structure with single 36 Å terraces that are separated by step bunches and confine surface electrons [1]. (Figure 1) ii) Ag/Cu(111): adsorption of Ag on vicinal Cu(111) surfaces lead to a variety of structures such as stripes, facets and overlayers. At the submonolayer regime, besides the chemical contrast, we find exotic electronic states and reconstruction patterns (misfit dislocations) that vary as a function of step spacing and coverage [2]. We plan a careful, thorough study using Ag wedges and well-oriented curved Cu crystals (Figure 2). Fig. 1: Characteristic STM images from vicinal Au(111) surfaces to be used as substrates for one-dimensional supramolecular self-assembly. Left, Au(788) (step arrays+fcc/hcp periodic patterns) and right, Au(433) (periodic faceting). On top, schematic sideview description of the surfaces. Figure 2: STM images (100 nm2) showing the variety of Ag/ Cu nanostructures with distinct structural and electronic properties that can be produced by Ag deposition on vicinal Cu(111) surfaces by varying Ag thickness, step type and surface orientation. In the right panel we show the schematic description of the wedge/curved crystal approach that permits step type, density and coverage variation in a single sample. a) Molecular assemblies: The current CRP work (STM/Photoemission/Absorption in collaboration with partners at Kiel, Berlin and Madrid), using plain fullerenes and linear, planar aromatic molecules with a whole variety of vicinal surfaces and templates, is expected to provide the clues about the basic experimental procedures, such as measurement conditions and limitations, as well as fundamental knowledge on the stability of substrates upon molecule adsorption and the kinetic parameters for different assemblies. 2.2. First year (2007): Overall set-up of the High Resolution Photoemission System: The correct characterisation of complex molecular structures which exhibit a succession of long-range, ordered phases require the combined use of powerful techniques. This will be achieved in Ortega’s group by combining, in a single vacuum system, Scanning Tunneling Microscopy/Spectroscopy (STM, structural properties) and High Resolution, Angular Photoemission (HR-ARPES, electronic properties). The latter will be incorporated in the existing chamber and tested with current molecule/surface systems: fullerene and benzodiguanamine on Au vicinals. The combination of STM/HR-PES is of particular importance in the study of diluted, ordered phases, induced by weak molecule/molecule interactions, such as dipole interactions, or forced by the structure (reconstruction patterns) or the electronic states of the substrate. Dilute ordered phases are inherently complex, i.e., they exhibit large unit cells (beyond 50 Å) and small interacting energies (in the meV range), thereby requiring both STM in real space and HR-ARPES with high wave vector (angular) and energy resolution in reciprocal space. Fig. 3: Differnt types of functionalized molecules to be tested for onedimensional supramolecular assembly. From left to right and from top down: Benzodiguanamine, 4-{[4-(pyridin-4ylethynyl)phenyl]ethynyl}benzoic acid, PCBA, INDAN, BINDAN First deliverable: Full characterization of fullerenes and benzodiguanamine assemblies on Au vicinals and Ag/Cu templates 2.2. Second-Third year (2008-2009): a) Planar aromatic molecules (Fig. 2): Synthesized by AP1. Currently we are working on aromatic molecules with symmetric end group functionalisation: benzodiguanamine (amine end-group) adsorption on Au(778) and Au(788), and plan to generalize the study to PTCDI and NTCDI (imine end-group) and to Au(433) and Ag/Cu stubstrates. We will investigate all coverage regimes, from dilute to monolayer saturation by means of the STM/HR-PES approach. Absorption/Photoemission experiments in collaboration with IP3 and IP4 are alredy being planned and will be implemented at BESSY/ELETTRA. Secondly we plan to study asymmetric hydrogen bonding introducing the study of linear pyrazole-carboxyliclike molecules with asymmetric single end-group (acid, pyridine), such as the one shown in Fig. 3, and also perform coadsorption experiments of imide and amine-like molecules, which are expected to strengthen the molecule/molecule interaction [3]. In a more advanced phase, the strategy of coadsorbing distinct molecules to strengthen intermolecular interactions will be tested in Hexa-tert-butylphenilbenzene- like molecules with amine and pyridine end groups. These are bulky molecules that are expected to exhibit weak substrate-molecule interactions (see AP1-C1). Second deliverable: Full characterization of NTCDI, PTCDI, and pyrazole-carboxylic-like on Au vicinals and Ag/Cu templates. Full characterization of coadsorbed NTCDI-benzodiguanamine on Au vicinals and Ag/Cu templates. Test of molecules of the family of Hexa-tert-butylphenilbenzene with pyridine, imine end groups, and coadsorption on Au vicinals and Ag/Cu templates. b) C60 and C70 fullerenes: Our current STM/Photoemission/Absorption experiments of C60 and C70 fullerenes on Au(788) encourage the use of functional groups and doping to modify molecule/molecule interactions. The fcc/hcp reconstruction pattern of Au(788) forces a periodic, selective clustering in fcc patches during monolayer completion [4]. These exhibit different degrees of substrate-induced metallicity, as revealed in photoemission/absorption experiments [5]. In a first step we will use synthetic PCBA, with an acid end-group expected to create stronger hydrogen bonding between molecules. As dopants, we will use alkali metals (K, Na). Photoemission/Absorption will be done in collaboration with IP2 and IP6 in the SLS. In a more advanced phase we will test other fullerene functionalizations, such as the polar BINDAN and INDAN molecules (synthesized by IP5), or thiol groups. Third deliverable: Full characterization of functionalized and doped fullerene assemblies on Au vicinals and Ag/Cu templates. 3.- Justification of major budget items Self-assambled supramolecular structures exhibit an inherent degree of complexity, namely large, complex building-blocks (unit cells) and small interaction energies. In practice, systems are difficult to characterize with standard electron diffraction techniques, and hence the combination of powerful, sensitive techniques in both real (STM) and reciprocal space (photoemission) is necessary. The current proposal is intended to incorporate state-of-the-art high resolution, angular Photoemission (HR-ARPES) to the current set-up in San Sebastian, which includes Variable Temperature STM and standard electron diffraction techniques. The HRARPES equipment consists on a display-type electron analyzer that allowing simultaneous measurement of angle-resolved spectra within a 5º range, a plasma-discharge lamp and a monochromator. Only the full equipment ensures energy resolution below 10 meV and angular resolution down to 0.1º. The former is necessary for the small interacting energies (narrow bands and gaps), whereas the latter is critical to resolve band structures for extended states in large unit cells (for instance, to explore substrate mediated interactions): in fact, with the standard photon energy of 21 eV, the angular resolution becomes 0.005 Å-1, and hence assuming 10 points per Brillouin zone, the equivalent spatial resolution goes beyond 10 nm. 2.- References [1] A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de Abajo and J. E. Ortega, Phys. Rev. Lett 87, 107601 (2001); A. Mugarza and J. E. Ortega, J. Phys. Cond. Mat. 15, S3281 (2003); J. E. Ortega , M. Ruiz-Osés, J. Cordón, A. Mugarza, J.Kuntze, and F. Schiller, New Journal of Phys. 7, 101 (2005). [2] J. Lobo, E. G. Michel, A. Bachmann, S. Speller, J. Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602 (2004); F. Schiller, J. Cordón, M. Ruiz-Osés, and J. E. Ortega, Phys. Rev. Lett 95, 066805 (2005). [3] J. A. Theobald et al., Nature 424, 1029 (2003). [4] N. Néel, J. Kröger, and R. Berndt, Adv. Mater., accepted for publication (2005). [5] F. Schiller et al. (unpublished). IP1 - B.2 CRP Acronym: MOL-VIC PI Name & Institution: Enrique Ortega, Universidad del País Vasco IP Nr:1 Funding Agency: Ministerio Educación y Ciencia (Spain) Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short Description of each budget item where appropriate Salary position Ph.D. student Post-doc. researcher senior researcher Technician student stipend / student assistant Equipment per item item 1 133400 item 2 133400 item … Electron analizer Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Conferences, workshops 4000 4000 4000 12000 Small parts, samples, evaporation material 4000 4000 4000 12000 26866 1520 1520 29906 Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads 19% if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 168266 9520 9520 187306 IP1.- B3 RELATED PROJECTS In general all the research work in San Sebastian is related to the study of electronic states in low dimensional systems, such as quantum wells, vicinal surfaces and, in general, laterla nanostructures. More information can be found at the Lab web page: http://dipc.ehu.es/nanolab There are two differnt on-going projects related to the subject of the present proposal. The first one “One-dimensional molecular self-assembly on vicinal surfaces”is the current CRP of the SONS Eurocores. It represents the fundamental, basic search on molecules/templates, which is necessary to carry out the projected activities of the new CRP SONS Eurocores. The second one “Caracterización experimental de la respuesta electrónica y óptica de nanoestructuras y sistemas de baja dimensionalidad” is a Spanish Ministry funded project on similar subjects, where molecular structures are investigated in the context of the electronic and optical response. It is a collaborative research work with different theoretical groups in San Sebastian, and from which we obtained a partial funding for the HR-PES equipment (30000 Euro) Ther is also an on-going collaboration with Prof. Nazario Martin from the Faculty of Chemistry of the Universidad Complutense de Madrid, who synthesizes fullerenes and PCBA molecules that are being currently tested in San Sebastian. IP1.- B4 OTHER SCIENTIFIC COLLABORATIONS In the context of the physics of low dimensional, metallic structures we keep a long-time collaboration with Prof. Himpsel’s group in the University of Wisconsin and the Synchrotron Radiation Center in Madison, Wisconsin. In such collaboration we basically focus on electronic states of Au/Si systems and magnetic layers. In the context of magnetic overlayers and nanostructures we keep an on-going collaboration with Prof. Daehne’s and Prof. Laubschat’s groups, from Berlin and Dresden, respectively. In the latter case, we take advantage of the collaboration to punctually carry out photoemission experiments in BESSY an at the Lab in Dresden. With respect to theory, Ortega’s group is strongly linked to the Solid State theory group in San Sebastian (http://dipc.ehu.es/group/index.htm), such as A. Rubio (first principles elctronic structure, spectroscopy) and F. J. García de Abajo (electrodynamics). Related to this project, we plan to collaborate with A. Arnau (STM modelling) and D. Sánchez-Portal (molecular dynamics). IP2-B1 PI: Richard Berndt, Universität Kiel a) Aims and objectives IP2 aims at the fabrication of linear molecular structures with controllable properties such as specific nearest-neighbour separation between molecules suitable for polymerization and thus for fabrication of unfolded proteins and other linear polymers with pronounced one-dimensional character of the electronic states. Moreover, the ordering of chiral molecules on a chiral vicinal surface will be investigated. We will further study geometric and electronic properties of endohedral fullerenes at the single-molecule level. b) Methodologies / Experiments Pristine metal vicinal surfaces as well as molecular templates developed during the previous funding period will be used, thereby providing a full variety of length scales and chemical affinities. Molecules will be custom-designed within the network in IP5 and AP1. Endohedral fullerenes will be analysed together with IP6. The systems are analysed by scanning tunnelling microscopy and spectroscopy at low temperatures (4 K, 50 K, 80 K). c) Workplan (1) C60 meshes and wires as templates We propose to use Au(788)-C60 and Au(433)-C60 as templates to guide subsequent adsorption of functional units. We have fabricated fullerene nanomeshes of rectangular fullerene islands (comprised of four fullerene chains, four to five C60 molecules each) on Au(788) with an extraordinarily high periodicity in two dimensions [1]. On Au(433) we have achieved an alternation of long and narrow fullerene and gold stripes [2]. (1.1) Polymerisation of fullerene nanostructures Polymerisation of C60 layers on surfaces is of considerable interest concerning the use of fullerenes as material-resistive masks for high-resolution photolithography [3]. Typical distances between our fabricated fullerene nanostructures are 10 to 50 nm. Since Rao et al. [4] first demonstrated polymerisation of C60 films by UV irradiation at room temperature, there have been several reports on fullerene dimers or polymers formed by various methods such as photoirradiation, high-pressure compression at high temperature, alkaline-metal doping, and electron impact [5]. The light-induced chemical reaction, which leads to the dimerisation of fullerene molecules is of the [2+2]-cycloadditional type [6,7]. The polymerisation was found to occur below a certain threshold wavelength and only when the molecules were able to rotate, i.e., above the merohedral temperature, which is usually around 250 K [8]. We will therefore use UV irradiation (160 - 370 nm, 0.1 W/cm2) to achieve polymerisation of the fullerene nanostructures on Au(788) and Au(433). A UV lamp with these specifications was successfully used by Nakayama and coworkers to polymerise a fullerene layer [9]. (1.2) “Linear protein” We propose to adsorb suitably functionalised amino acid (lysine) on the fullerene nanowires in order to achieve a linear arrangement. Adsorption of amino acids on solid surfaces under ultra-high vacuum conditions has been shown for, e.g., Cu(110) [10,11]. A subsequent irradiation of the adsorbate system with UV light (see specifications in (1.1)) will induce polymerisation of the amino acid molecules, which may lead to the formation of an unfolded protein. If successful this preparation would open an avenue for fascinating experiments on protein folding. (2) Polymer formation from diynes and oxazolidin-2,5-dion In addition to the approach presented above, which relies on C60 templates we will explore an alternative route to prepare linear molecular wires and proteins. We will adsorb diynes synthesised by IP5 on vicinal surfaces in an attempt to fabricate linear arrays, which are then then polymerised by UV light irradiation (see specifications of the UV lamp in (1.1)). As a result polyacetylenes are obtained, which are semiconducting molecular wires consisting of a single C-C backbone. These ultimately thin molecular chains may be used as wires in molecular electronics. Moreover, we expect oxazolidin-2,5-dion to arrange in linear arrays. Again, polymerisation will be attempted with the goal to fabricate an unfolded protein. If it turns out that the molecules do not stick to the surface then they can be chemically modified (attachment of an aromatic residue) by IP5 to meet the adsorption requirements. (3) Adsorption of chiral molecules on chiral metal surfaces Chiral assemblies are particularly interesting for their ability to induce enantioselectivity in catalytic reactions [12] and for their unique optical [13] and electronic properties [14]. A way to trigger enantioselectivity is to use vicinal, kinked surfaces that are intrinsically chiral substrates for adsorption [15]. But also achiral substrates can become chiral, either by adsorption of chiral molecules as in the case of tartaric acid on Cu(110) [12] or by chiral restructuring upon adsorption, as demonstrated for (achiral) hexa-tert-butyl-decacyclene (HtBDC, C60H66) molecules on Cu(110) [16]. Such local restructuring has been proposed to be one of the key ingredients in understanding phenomena as chiral recognition, which are believed to be fundamentally relevant for enantiospecific catalysis [17]. Here we propose to adsorb chiral molecules (tartaric acid, Cu-tetra-3,5 di-ter-butyl-phenyl porphyrin (CuTBPP)) onto Au(16,14,15). This is a first attempt to study a surface with a high density of kinks, and hence potential chirality. Indeed, the miscut angle of the substrate has been chosen to tune single-domain, zig-zag, reconstructed terraces, with preferential adsorption sites at corners. Depending on the observations, other kinked surfaces will be tested to optimise domain size. (4) Investigation of endohedral fullerenes Endohedral fullerenes, which are closed-cage carbon molecules with embedded atoms or molecules are expected to be important for molecular electronics [18]. As a consequence the fabrication of endohedral fullerene wires is of importance. To fabricate arrangements of endohedral fullerene chains, adsorption on Au(788) will be performed as a first experiment. In cooperation with IP6 we will investigate the adsorption of endohedral fullerenes on surfaces. While IP6 will study structural aspects of the adsorption and the electronic properties of H2@C60 (a hydrogen molecule is incorporated in a fullerene cage) with photoemission, we aim at the discrimintation of the electronic structure of single H2@C60 from C60 with low-temperature scanning tunnelling microscopy and spectroscopy. In particular we plan to analyse the vibrational properties of H2 in C60 cages using inelastic tunnelling spectroscopy. d) Deliverables Month 12: IP2 reports on progress in polymerisation of fullerene nanostructures on vicinals. IP2 reports on adsorption of amino acids and diynes . Month 24: IP2 reports on adsorption of oxazolidin-2,5-dion. IP2 reports on polymer formation of molecules mentioned above. Month 36: IP2 reports on adsorption of chiral molecules on chiral surfaces. IP2 reports on adsorption of endohedral fullerenes on vicinals and the whole project. e) Justification for budget items Staff: The complexity of the planned experiments along with the interdisciplinary aspect of the work requires a post doctoral researcher. Equipment: To induce polymerisation an UV lamp (Lot-Oriel, 160-370 nm, 0.1 W/cm2) is required along with a power supply. The light will be focussed onto the sample in ultra-high vacuum using UV-grade lenses (Melles Griot), which can be approached to the sample by a translation stage (MDC). References [1] N. Néel, J. Kröger, and R. Berndt, Adv. Mater., accepted for publication (2005). [2] N. Néel, J. Kröger, and R. Berndt, Appl. Phys. Lett., submitted (2005). [3] A. F. Hebard, C. B. Eom, R. M. Fleming, Y. J. Chabal, A. J. Muller, S. H. Glarum, G. J. Pietsch, R. C. Haddon, A. M. Mujsce, M. A. Paczkowski, G. P. Kochanski, Appl. Phys. A: Solids Surf. 57, 299 (1993). [4] A. M. Rao, P. Zhou, K.-A. Wang, G. T. Hager, J. M. Holden, Y. Wang, W.-T. Lee, X.-X. Bi, P. C. Eklund, D. S. Cornett, M. A. Duncan, and I. J. Amster, Science 259, 955 (1993). [5] M. S. Dresselhaus, G. Dresselhaus, and P. C. Eklund, Science of Fullerenes and Carbon Nanotubes (Academic, New York, 1996), p. 106, and references therein. [6] M. R. Pederson and A. A. Quong, Phys. Rev. Lett. 74, 2319 (1995). [7] C. H. Xu and G. E. Scuseria, Phys. Rev. Lett. 74, 274 (1995). [8] W. I. F. David, R. M. Ibberson, J. C. Matthewman, K. Prassides, T. J. S. Dennis, J. P. Hare, H. W. Kroto, R. Taylor, and D. R. M. Walton, Nature (London) 353, 147 (1991). [9] T. Nakayama, J. Onoe, K. Nakatsuji, J. Nakamura, K. Takeuchi, and M. Aono, Surf. Rev. Lett. 6, 1073 (1999). [10] E. M. Marti, S. M. Barlow, S. Haq, and R. Raval, Surf. Sci. 501, 191 (2002). [11] Q. Chen and N. V. Richardson, Nature Materials 2, 324 (2003). [12] M. Ortega Lorenzo, C. J. Baddeley, C. Muryn, and R. Raval, Nature (London) 404, 376 (2000). [13] T. Verbiest, S. Van Elshocht, M. Kauranen, L. Hellemans, J. Snauwaert, C. Nuckolls, T. J. Katz, and A. Persoons, Science 282, 913 (1998). [14] K. Ray, S. P. Ananthavel, D. H. Waldeck, and R. Naaman, Science 283, 814 (1999). [15] Ch. McFadden, P. Cremer, A. Gellmann, Langmuir 12, 2483 (1996). [16] M. Schunack, L. Petersen, A. Kühnle, E. Lægsgaard, I. Stensgaard, I. Johannsen, and F. Besenbacher, Phys. Rev. Lett. 86, 456 (2001). [17] A. Kühnle, T. R. Linderoth, B. Hammer, and F. Besenbacher, Nature (London) 415, 891 (2002). [18] S. Kobayashi, S. Mori, S. Iida, H. Ando, T. Takenobu, Y. Taguchi, A. Fujiwara, A. Taninaka, H. Shinohara, and Y. Iwasa, J. Am. Chem. Soc. 125, 8116 (2003). IP2 - B.2 CRP Acronym: MOL-VIC PI 2 Berndt, Kiel University: IP Nr: 2 Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding Short Description of each budget item where appropriate (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Complex experiments with interdisciplinary aspects 56000 56000 56000 UV-lamp setup for polymerisation experiments 19700 Salary position Ph.D. student Post-doc. researcher 168000 senior researcher Technician student stipend / student assistant Equipment per item item 1 19700 item 2 item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) 4000 4000 4000 12000 5000 5000 5000 15000 Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 84700 65000 65000 214700 IP2.- B3 RELATED PROJECTS As evident from our recent publications our work revolves around spectroscopy of individual atoms, molecules and clusters. In terms of funding, the only project related to MOLVIC is Scanning Tunnelling Microscopy of metal-chalcogenides and organic molecules in the framework of the “DFG Forschergruppe 353”. More information can be found at the Lab web page: http://www.ieap.uni-kiel.de/surface/ag-berndt/. IP2.- B4 OTHER SCIENTIFIC COLLABORATIONS We have a number of scientific collaborations which are reflected by the more recent publications. S. Crampin (Bath, UK) is performing various electronic structure calculations related to our experimental results. P. Johansson (Örebro, Sweden) performs numerical modelling of light emission from the STM and of the impact of the STM tip on electronic states. W. Hofer (Liverpool, UK) supports us with total energy calculations for our transport experiments on single atoms. M. Brandbyge (Copenhagen, Denmark) calculates inelastic effects in molecular transport related to our recent experiments on single molecules (unpublished work). N Lorente (Toulouse, France) investigates molecular interactions in order to interpret our data on orbital shifts of organic molecules in two-dimensional meshes. The group of P. Echenique (San Sebastian) has provided continuous backing in interpreting electron dynamics at surfaces. There is an on-going collaboration with R. Wiesendanger (Hamburg, Germany) on spin-polarised tunnelling. Locally, in Kiel, we cooperate with groups in the theoretical physics department, from the “Technische Fakultät” and from the chemistry department in an initiative for a “Sonderforschungsbereich” on switching processes of organic molecules at surfaces. IP3-B1 PI: Enrique García Michel, Universidad Autónoma Madrid Substrate-mediated self-assembly of organic molecules: structural and electronic properties 1-IP AIMS AND OBJECTIVES: Building up a functional structure exploiting self-organization requires a detailed understanding of the self-organization process itself. Both physical and chemical properties and the equilibrium structure of a self-organized system depend on the interactions between the molecular components and with the supporting substrate. Controlling the self-organization process requires to understand the interactions at nanoscopic level (intermolecular and molecule-substrate), their hierarchy and the influence of kinetic parameters. Taking into account the complexity of the self-organization process, and the wide range of interactions playing a role, it is important to analyze a variety of model systems, which can provide information on each aspect of the process. The main goal of this IP is to understand the different modes of intermolecular interactions mediated by the substrate. This means that we are considering dilute systems (where the mean intermolecular distance is beyond the reach of direct interactions), and /or molecular species which do not exhibit stronger direct interactions, like hydrogen bonding. This kind of systems are less common than supramolecular structures where direct bonding takes place, but can be very interesting. There exist different mechanisms for substrate-mediated interactions. A long-time known mechanism for atomic selfassembly is long-range (10–30 nm) surface-state-mediated adatom interaction 1, which is known to operate on metal surfaces2. The adatom acts as an impurity, and the surface state electrons try to screen it. This produces surface state Friedel oscillations. Not all wave vectors contribute to the screening process, because of the cutoff at the Fermi energy 3. As a result the local density of states at the Fermi energy oscillates around the impurity with a wavelength of F/2=/kF, where F is the Fermi wavelength and kF the Fermi wave vector. The variation of the local density of states at E F due to standing-wave formation modifies the adsorption energy of the adsorbates. Regions of high local density of states are favoured for adatoms. Thus, the interaction between the adsorbates, and consequently their mutual distance, is determined by the LDOS at EF. The interaction energy decays as 1=r2 where r is the distance between two adatoms, and oscillates with a period of F/2, half of the Fermi wavelength of the surface-state electrons. A first goal of this IP is checking the extension of this mechanism to supramolecular ordering. Preliminary results for pentacene adsorption on Cu(110) indicate that a surface-state mediated interaction might be playing a crucial role in the formation of pentacene superstructures. We expect that surface state mediated interaction dominates the supramolecular ordering for adequate metallic substrates and for molecules which are not suitable for directional intermolecular interactions, as hydrogen bonds. This is the case of simple aromatic molecules like pentacene or anthracene, but also of more complex molecules. The use of vicinal noble metal surfaces provides us with an additional degree of freedom, because the properties of the surface state can be tuned by changing the miscut angle 4, and thus different regimes can be probed. In turn, this can be used to understand the details of the interaction. For instance, although there is no known case of formation of supramolecular ordering mediated by the electrons confined at the terraces, this is certainly possible, and it will be explored along this IP by using vicinal noble metal surfaces. A second mechanism for substrate-mediated self-ordering is related to the existence of elastic interactions. In general, the formation of periodic structures involves an energy cost, related to the formation of boundaries. Models based on linear elasticity theory predict that the elastic energy gained in the bulk by the formation or alternate domains with different surface stress might be sufficient to pay back the energy cost of boundary formation. This mechanism seems to be acting in the faceting of vicinal surfaces and in the formation of stripes upon oxygen adsorption on Cu(110) 5. The case of N on Cu(100) is somewhat more complex, but can be explained on the same grounds. There is also direct evidence for the effect of local surface strain on the bonding strength for adsorbates6. It is a natural extension of all these observations that the local strain field modifies the adsorption energy of more complex molecules. Obviously, the mechanism is not straightforward, since any modification of the strain will also affect the local electronic structure7. In this IP we intend to explore the role of local strain, 1 K.H. Lau and W. Kohn, Surf. Sci. 75, 69 (1978). J. Repp et al, Phys. Rev. Lett. 85, 2981 (2000). 3 P. Hyldgaard and M, Persson, J. Phys. Cond. Matt 12, 13 (2000). 4 J.E. Ortega et al. Phys. Rev. Lett. 84, 6110 (2000). 5 V. Repain et al, Phys. Rev. Lett.84, 5367 (2000) ;K. Kern et al, Phys. Rev. Lett. 67, 855 (1991). 6 M. Gsell et al, Science 280, 717 (1998). 7 D. Sekiba et al, Phys. Rev. Lett. 94, 016808 (2005). 2 and substrate structure modification upon adsorption, in the formation of complex, long-range ordered superstructures. Vicinal surfaces already characterized along the current CRP offer an excellent playground for studies of this kind, since the terrace size and other structural parameters of the substrate can be tuned. 2-METHODOLOGIES/EXPERIMENTS: The complexity of the physical effects analysed requires a multi-technique approach in order to probe simultaneously the structural and electronic properties of the system. The generic objective of the IP (to understand the mechanisms which rule the self-organization of diluted systems) requires the analysis of two different properties: Structural properties, to determine the nature of the long-range order in the self-organized systems, including both the superstructure geometry and the possible modifications of the substrate structure, and electronic properties, to understand the role of the electronic structure in the self-organization process. Low-energy electron diffraction (LEED) will be used to study the long range order of superstructures grown on vicinal templates. LEED has many advantages with respect to other structural techniques, like its high surface sensitivity and its readiness as a conventional laboratory technique. Its main disadvantage is the possible sensitivity of organic molecules to the electron beam, and also the complexity of the superstructures induced by molecular self-assembly, which tend to exhibit large unit cells. Both problems are to be overcome by the use of spot-profile LEED (SPALEED). On the one hand, the use of channeltron amplification enables the use of much lower electron currents (in the range of 500 pA). On the other hand, the large transfer width of SPALEED enhances the resolution and facilitates the analysis of complex superstructures. An SPALEED apparatus will be available soon in our laboratory, and it will be integrated with our current ARPES spectrometer, already operational, which comprises a high-flux He-plasma UV source, a hemispherical electron analyzer and a cryogenic manipulator with 5 degrees of freedom. The energetic resolution of this setup is 30 meV and the angular resolution is 0.5º (equivalent to a k-space resolution of 0.03 Å-1 approximately, which enables us to probe unit cells in the range of 3-4 nm. The integration in the same apparatus of ARPES and SPALEED constitutes a powerful combination of probes of reciprocal space, sensitive to both structural and electronic properties. While STM provides local structural information, such as molecular adsorption sites and conformation, SPALEED is sensitive to long range order. We note that a crucial step for the success of our approach is the combination of the structural information provided by SPALEED and by STM (IP1, IP2). While SPALEED is the technique best adapted for the overall problems we are going to face, we are also familiar with other structural techniques, which will be used if necessary. In particular, surface x-ray diffraction can be useful to analyze the minor modifications induced in the substrate by molecular adsorption. Photoelectron diffraction (IP6) is also useful whenever there is no long-range order, but there is a well-defined local molecular adsorption geometry. It is also sensitive to local modifications of the substrate induced by the adsorption. 3-WORK PLAN AND MILESTONES We consider both scientific activities and instrument implementation. SCIENTIFIC ACTIVITIES Activity 1: Template production and characterization (YEAR 1) The goal is to obtain templates which offer different periodicities and electronic structures, suitable to test the molecular assembly for a variety of controlled situations. We restrict ourselves to substrates without a direct chemical reaction with the adsorbates, since the deposited molecular species should remain stable. The substrates of choice are single-crystalline vicinal noble metal surfaces. A previous characterization by STM of the substrate properties will be undertaken by IP1 and IP3, or it has already been done along this project. In any case, an in situ characterization with LEED and SPALEED will enable a quantitative analysis of the substrate structure and the availability of templates with reproducible properties. Milestone: obtaining a broad range of well-characterized substrates with tunable structural and electronic properties. Activity 2: Molecular assembly: structural properties (YEAR 1-2) Molecular assembly will be analyzed using the substrates obtained from Activity 1. We are experienced in the use of vicinal noble metal surfaces. The variety of structural parameters which can be modified (terrace size, nature of the step, azimuthal orientation of the step, etc) will facilitate the selection of the substrate most adequate for each type of molecule. For instance, one dimensional self assembling along terraces requires a terrace size significantly larger than the molecular size. Furthermore, tuning the terrace size by changing the miscut angle modifies also the surface electronic structure in a controlled manner, which can be used to test the mechanisms of the substrate mediated interaction. Activity 2.1: Substrate mediated molecular assembly We plan to analyze the nature of the assembling process by studying aromatic molecules adsorbed on vicinal surfaces with large terraces. The terrace widths will be used to tune the substrate electronic properties and find a correlation with the molecular superstructures observed. Milestone: obtaining long-range ordered self-organized structures for aromatic molecules for different terrace widths. Characterization of their structural properties using SPA-LEED. Activity 2.2: Structural modifications of the substrate after adsorption An important aspect of the molecule-surface interaction is the structural modification of the substrate to optimize adsorbatesubstrate chemical bonding. This effect can become very important, giving rise to a true deformation of the substrate to adapt it to the molecule. The structure can be analyzed using SPALEED; but it is possible that an analysis using photoelectron diffraction (IP3) is needed, since this technique is better adapted to the analysis of local deformations. Milestone: developing routine tools to characterize the substrate deformation for simple aromatic molecules of different lengths. Activity 3: Molecular assembly: electronic properties (YEAR 2-3) Angle resolved photoemission will be used to study the electronic structure of the template and of the molecular superstructure. The main goal of this IP is to understand and evaluate the substrate mediated interaction. To this end, an analysis of the electronic structure before and after adsorption is crucial. As already observed by us, a long-range ordered molecular superstructure can either induce new surface states, or modify the periodicity, filling and reciprocal space location of already existing surface states. All these changes induce a more favourable electronic structure, which in turn facilitates the formation of certain molecular superstructures. Milestone: developing routine tools to characterize substrate deformation for aromatic molecules of different lengths. INSTRUMENT IMPLEMENTATION Activity 4: put into operation of new UHV chamber (YEAR 1) Design, acquisition and put into operation of a ultra-high vacuum chamber dedicated to the exposure to molecular adsorbates. The chamber should have an independent pumping system, evaporators of Knudsen cell type, a manipulator compatible with the current transfer system of the chamber and a quadrupole mass spectrometer (QMA), which will be used to test the purity of the residual gas and the adsorbates. A conventional LEED apparatus will be installed as well for a rapid test of superstructure formation. Milestone: put into operation of a UHV chamber dedicated to molecular exposure. Activity 5: put into operation of SPALEED diffractometer (YEAR 1) Put into operation of low-energy electron diffractometer with spot profile analysis, adapted to the study of complex surface periodicities. Development of adequate software tools. Milestone: put into operation of the SPALEED apparatus. 4-JUSTIFICATION FOR BUDGET ITEMS The development of the scientific objectives described above requires very strict experimental conditions. In particular, the process of molecular evaporation must be done in a dedicated UHV chamber, in order to avoid damage to the instruments of the main chamber and to guarantee controlled preparation conditions. Sample preparation (ion gun, sample heating) are needed in this chamber also. A QMS is also required to guarantee the quality and cleanliness of the molecular evaporations. An important budget item is the application for the salary of a postdoctoral researcher. The development of the activities described in the project represents a significant increase of the work load, which cannot be undertaken without additional manpower. The postdoctoral researcher hired will take care of the operation of the SPALEED, data acquisition and analysis, with support from the rest of group. He/she will also be involved in the whole research activities related to this IP. IP3 - B.7 CRP Acronym: MOL-VIC Outline Proposal Nr(s).: 05-SONSOP-014 BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Salary position Post-doc. researcher Equipment per item Item 1 Item 2 Item 3 E.G: Michel, Universidad Autónoma de Madrid Funding Agency: Minist. de Educación y Ciencia (Spain) IP Nr:3 Duration where appropriate in month, including start date 24,1.1.2008 YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding Short Description of each budget item where appropriate (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] 35360 35360 Salary of post-doc researcher 70720 Quadrupole Mass Spectrometer UHV chamber and UHV gauge Turbo and rotary pumps, gate valve Transfer rod 20000 20000 12000 20000 20000 5000 5000 Conferences, workshops, 2000 2000 2000 6000 Small parts, samples, evaporation material 2000 2000 2000 6000 Publication, Dissemination Costs Publication costs Overheads 19% 0 9310 1000 9948 1000 7668 2000 26927 1000 1000 1000 3000 Item 4 Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs 12000 including analysis costs if applicable Others Travel to synchrotron radiation facilities including access to large infrastructures, shiptime, etc. (please specify) T O T A L 59310 63308 49028 171647 IP3.- B3 RELATED PROJECTS We have successfully conducted during last years a significant number of research projects and research contracts, both at national and international levels. An important scientific production is derived from this activity: more than 80 publications in international journals since 1997, a similar number of contributions to conferences (many of them invited and frequently chairing sessions), six PhD thesis successfully finished, and two more being currently done. The current MOL-VIC application is the continuation of our on-going MOL-VIC project. With the exception of this project, which we do not describe here, there is no direct relationship with other already funded or applied for projects, besides the fact that all the projects are related to the investigation of the electronic structure of surfaces and interfaces. In particular, the role of the electronic energy in the stabilization of low-dimensional structures has been analyzed in several different model systems, a topic related in part to our contribution to MOL-VIC. In recent years our research has focused in two different topics related in part to the subject of this application: 1- Role of electronic effects in the formation of collective states at surfaces. In this general topic we have analyzed a) 2D structural phase transitions and electronic effects: we have studied several model systems, like K/Si(100), where different effects compete to determine the metallic character of the surface, giving rise to a complex experimental phenomenology. We have also studied the surface of Sn/Si(111) as a function of coverage in the range of formation of a solid solution of (3x3)R30º structur. We observe in this surface a metal/semiconductor transition as a functions of coverage, related to the existence of a small charge transfer between Sn and Si at low coverage. b) Surface charge density waves: several years ago, the existence of a surface CDW in Sn/Ge(111) and Pb/Ge(111) was proposed. We have studied these two systems using several different techniques. Our analysis of the evolution of the electronic structure of the system with temperature, of the structure of the low temperature phase, and finally the observation of a soft phonon related with the transition, allowed us to demonstrate that the phase transition is much more complex than expected, but it is not related to CDW stabilization. 2-Quantum confinement effects at surfaces a) Quantum Well Status and electronic growth: in previous works we have demonstrated the existence of several periodicities of QWS, and we have also studied other properties of these systems. More recently, we have analyzed the use of QWS as a sensitive probe to analyze final state bands. b) Electronic structure of laterally nanostructured systems: we have studied the electronic structure of Cu(223) and Ag/Cu(223). In this case, the layer of Ag generates a surface with facets which produces lateral confinement of the electron surface states. We have also studied as model system the stepped surfaces of Cu(111), where we detect a change in the nature of the electron wave function of the surface state, related to the lateral periodicity of the surface. Self-organization at surfaces has been exploited as a way to produce long-range ordered nanostructures. IP3.- B4 OTHER SCIENTIFIC COLLABORATIONS We participate in several different international collaboration programmes. Through these programmes we have successfully developed collaborations with the following groups (we exclude here collaborations within the MOL-VIC project): 2- K. Wandelt, at the Institute for Theoretical and Physical Chemistry of the University of Bonn, Germany. 3- P. Soukiassian, at the University of Paris-Sud and CEA, in France. 4- T. Balasubramanian, at the synchrotron radiation laboratory Max-Lab, in Sweden. 5- H. Ascolani, at the Atomic Center of Bariloche (Argentina). 6- G. Panaccione, at the TASC laboratory of CNR in Trieste (Italy). 25 IP4-B1 PI: Karsten Horn, Fritz Haber Institut, Berlin Low-dimensional molecular arrangements – electronic structure and chirality 1. Aims and Objectives At the center of interest in the group “PI Horn” is the characterization of the electronic structure of low-dimensional systems in its relation to morphology and molecular conformation on flat and stepped surfaces. Starting from a general characterization of complex organic molecules as demonstrated in previous work, we will move towards complex systems in which dimensionality is imprinted on the overlayers by means of suitable vicinal surfaces. The experimental methods are core and valence level photoelectron spectroscopy assisted by scanning tunnelling microscopy to ascertain the desired conformation of the overlayer-substrate system. Of particular interest in the continuation of the project will be two aspects of molecular structures on surfaces: a) the chiral nature of adsorbed species, and b) the change in molecular confirmation upon excitation with electrons and UV light. Both aspects within the general MOL-VIC framework are discussed in the detailed work plan below. 2. Methodology/Experiments The group has studied several molecular adsorbates on metal and semiconductor surfaces with a view to identifying the bonding interaction of simple organic molecules with metal and semiconductor surfaces. Recently, interest has moved on to identifying the chiral nature of molecules and molecular fragments on surfaces. Chirality is a fascinating aspect of molecular structure, not only from a fundamental point of view1 (e.g. a single handedness of practically all biologically active molecules), but also in view of applications. Enantiomeric purity of chemical products is of central importance in any production, for example2 (remember for example the thalidomide tragedy). Heterogeneous catalytic processes for enantioselective synthesis have important advantages over conventional homogenous ones. The induction of a chiral preference by coadsorption of so-called chiral “modifier” molecules is an important step in the heterogeneous catalytic conversion of pro-chiral reagents into one of the possible optical isomers.3 The problem is that the characterization of the chiral nature of adsorbed molecules is difficult; the usual method of optical rotation fails because of the low concentration of scatterers, and (on metal surfaces) because of the optical properties of the substrate. Certain spatial arrangements of molecules have been studied in STM, which are clearly induced by the chiral nature of the adsorbate. However, the detection of chiral centers by means of the widely used electron spectroscopies has so far proven elusive. Utilizing the access to circularly polarized x-rays at the BESSY storage ring, we have used circular dichroism in core level photoemission to identify the (R,R) and (S,S) forms of butanediol on Si(100)4. In both cases, a sizeable dichroic signal was found in the C15 spectra, which erased upon changing the enantiomer, and was absent when studying the achiral (R,S)-form of the molecules. There is a complication in such experiments due to an influence of the experimental geometry which may induce dichroism not related to the adsorbate, but this was avoided using a specific high symmetry geometry. Consider the data in Fig. 1 which clearly show the Fig. 1: a) Schematic view of the experimental geometry for circular dichroism experiments. b) Photoelectron spectra of the C 1s levels for the stereoisomers of 2,3-butanediol excited by right (dashed, blue) and left-circularly polarized (solid line, red) light. forms. c) Difference signal for the three stereoisomers. From ref. 4 . 26 reversal of dichroism in adsorbed butanediol. Work on adsorbed tartaric acid, the molecule in which Pasteur found the first evidence for such chirality, has begun and is expected to yield important data on the interplay between the chirality and different structural arrangements on the surface (mono- and bitartrate); this system is useful since, in contrast to butanediol, detailed structural data exist. Within the second topic, i.e. change in molecular conformation upon excitation with electrons and photons, work has been carried out on the characterization of biphenyl, in collaboration with the group of Prof. Dujardin, Paris. Prof Dujardin's group has recently demonstrated that in biphenyl adsorbed on Si(100), reversible molecular increments can be induced by resonant electronic excitation – different reversible and bistable movements were selectively activated by tuning the electron energy5. Such molecular switching may open up interesting applications in the field of molecular electronics. Our photoemission and NEXAFS data (work in progress) may serve to identify the bonding mechanism and conformation. Ultimately, we aim at using selective UV irradiation to induce movements in this socalled “molecular nanomachine”. 3. Work plan and milestones In the continuation of the project, four topics are at the center of interest. First, in all systems to be studied, photoelectron spectroscopy will be used to elucidate the electronic structure of the adsorbed molecules, which is central to an understanding of all aspects of the formation of supramolecular assemblies. From simple molecules such as stilbene and tartaric acid discussed below in a separate context, to the complex ones such as oxazolidin-2,5diones carboxy-hydroxamic acids preprared by Herges (IP 5), valence level spectra supported by quantum chemical calculations will shed light on the bonding mechanism and the influence of configurational changes in the adsorbed phase on the molecular orbital structure. Second, the aspect of molecular chirality on surfaces will be addressed on vicinal surfaces. We have recently studied the clean and metal-covered Si(557) surface, which consists of regular terraces, with a view to identifying the causes for a large anisotropy observed in electronic transport measurements. This vicinal template, and similar metal ones, will be used to study quasi-one-dimensional structures of chiral molecules on surfaces. Moreover, this work will be extended to vicinal surfaces where chiral centers in the clean surface can be prepared by a suitable miscut of the surface, to produce kinks. This will yield insight into the action of the surface to induce chirality in more complex organic molecules. This work will be carried out in a combination of STM and photoemission studies, using mainly silicon surfaces as templates. A close collaboration with IP 1 – Ortega for the use of well-defined vicinal surfaces, and with IP 2 –Berndt for the STM characterization of such chiral systems is mandatory for the successful realization of this project. Fig. 2: Molecular models for cis- and A third topic is the attempt to induce chirality into adsorbed achiral trans-stilbene. layers by using a kind of "doping" method. Recently, evidence was found for a process in which a small amount of chiral molecules may act to switch an entire achiral layer of succinic acid into a chiral form6. This surprising, apparently long-range action of a small amount of chiral modifiers may be important for the use in heterogenous catalysis, and may also shed light on the process of molecular recognition which probably needs an "amplification" stage. The fourth topic relates to the switching of molecules on surfaces induced, for example, by illumination with near-uv radiation. A number of studies have shown that a cis-trans isomerization in stilbene occurs in the gas phase (see molecular models in Figure 2), and mechanisms for this process have been proposed 7. This process may also occur, although following a different pathway, on solid surfaces, suggesting a variety of applications. The IP Horn is located in the Department of Molecular Physics of the Fritz-Haber-Institute, where laser sources are available to study such switching process as a function of several parameters (illumination wavelength, pulse length, polarization etc.) Starting from an analysis of pure cis- and trans-stilbene on surfaces, ways to identify the molecular conformation from its valence level spectrum, and from the adsorption geometry interpreted from NEXAFS will be 27 explored. This will lead to detecting such molecular switching processes in adsorbed stilbene. While these initial studies may also be carried out on flat surfaces, the continuation of the project, with various functional groups attached to the stilbene main building blocks, will benefit from the use of linear structures. Again, this work requires the characterization of the layers by STM, either in the home lab or in collaboration with IP 2, since the conformational changes induced by light are likely to be strongly influenced by terrace width and atomic structure of the substrate at steps and kinks, in the sense of a steric hindrance. Milestones: - completion of the study on the chiral nature of different structures of tartaric acid on Cu(110) - clarification of the "doping" action of chiral molecules in achiral adsorbed layers - investigation of complex adsorbed molecules, e.g. oxazolidin-2,5-diones and carboxy-hydroxamic acids - identification of the cis- and trans- conformation of stilbene on surfaces - demonstration of molecular switching induced by light in adsorbed stilbene layers - study of stilbene with functional endgroups. Deliverables – see work plan 4. Justification for budget items This work needs a fully dedicated postdoctoral researcher to tackle the complexity of the experiments involved, and the command of the different experimental efforts and interpretation methods. References 1. 2. 3. 4. 5. 6. 7. L.Pasteur, Ann.Chim. Phys. III, 24, 442(1848). I. Agranat, H. Caner, and J. Caldwell, Nat. Rev. Drug. Discov. 1, 753 (2002); T. P. Yoon and E. N. Jacobsen, Science 299, 1691 (2003). H. B. Fang, L. C. Giancarlo, and G. W. Flynn, J. Phys. Chem. B 102, 7311 (1998); R.Fasel, M. Parschau, and K.-H. Ernst, Angew. Chem. Int. Ed. 42, 5177 (2003). J. W. Kim, M. Carbone, J. H. Dil, M. Tallarida, R. Flammini, M. P. Casaletto, K. Horn, and M. N. Piancastelli, Phys.Rev. Lett., 95, 107601(2005). M. Lastapis, M. Martin, D. Riedel, L. Hellner, G. Comtet, G. Dujardin, Science 308,1000(2005). M. Parschau, T. U. Kampen, and K.-H. Ernst, Chem. Phys. Lett. 407, 433-437 (2005). W. Fuß, C. Kosmidis, W.E. Schmid, and S. A. Trushin, Angew. Chemie Int.Ed. 43, 4178(2004). IP4 – B2 CRP Acronym: MOL-VIC IP Nr: must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] 56.000 56.000 Short Description of each budget item where appropriate Fritz-Haber-Institut DFG Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS K.Horn PI Name & Institution: 4 Salary position Ph.D. student Post-doc. researcher Scientific experiments on senior researcher supramolecular structures on Technician surfaces 56.000 168.000 student stipend / student assistant Equipment per item item 1 item 2 item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) TOTAL 56.000 56.000 56.000 168.000 29 IP4 – B3 RELATED PROJECTS The group of the Principal Investigator has conducted, over the last six years,, a number of research projects aimed at understanding the electronic structure of low-dimensional systems, as well as complex metallic alloys. There are no related projects in this sense which are funded from national or international agencies. The PI is partner of the EU Network of Excellence "Complex Metallic Alloys" in which crystalline alloys with hundreds and thousands of atoms in the unit cell as well as quasicrystalline materials are investigated. IP 4 – B4 OTHER SCIENTIFIC COLLABORATIONS The principal investigator maintains a number of informal collaborations with German and EU groups in the field of adsorbed layers and low-dimensional systems, which do not, however, collide with the activities proposed in the continuation project. 30 IP5-B1 PI: Rainer Herges, Universität Kiel One-dimensional polymerization and attachment a) Aims and objectives “IP Herges” aims at the design and synthesis of compounds for the preparation of linear polymeric structures, such as polydiacetylenes and unfolded poteins, on a surface. Polydiacetylenes are fully conjugated molecules that exhibit interesting electronic properties such as conductivity and thus have the potential to be used as molecular wires. The polymerization of suitable precursors preorganized in a linear array leads to protein chains in a non-natural unfolded conformation providing the opportunity to study the biochemically important folding process. b) Methodologies / Experiments Chemistry and particularly chemical synthesis on metal surfaces is different from the traditional “wet chemistry”. To synthesize isolated linear polymers on surfaces, the monomers have to be designed in such a way that a self-propagating chain reaction in one or two dimensions can be initiated. E. g. diynes with an alkane spacer and a thiol end group and a long alkane substituent are forming self assembled monolayers suitable for photochemically induced polymerization. Oxazolinediones and malonic acid monoazides are suitable precursors for the protein formation under above conditions. One- or twodimensional arrangements of C60 will be used as templates for protein synthesis. To attach the amino acid lysine on C 60 the amino group in the side chain has to be converted to an azide. More functionalized fullerenes will be prepared by cyclopropanation via the Bingel reaction. The amino acid monomers and photoswitchable compounds have to be modified with thiol or dithiocarbamate groups to be attached to a gold surface. These compounds are not commercially available and have to be synthesized and optimized in our laboratory. Moreover, surface polymer chemistry is a relatively new field and has to be developed in specific areas by our group. Our compounds will be tested in close collaboration with the surface physicists “IP’s Bernd, Greber, Horn and Michel. c) Workplan (1) Polymerisation of amino acid derivatives on surfaces. In nature proteins are sequentially synthesized in the ribosome. Immediately after the protein chain leaves the ribosome it starts folding to the native structure. The folding process is difficult to study because so far there is virtually no way to prepare the linear starting structure and because the folding cannot be stopped and investigated in intermediary stages. A linear array of amino acid precursors on a surface polymerized to an isolated non-solvated protein chain would be a prototype starting configuration for the investigation of the folding process. Studies of the (electronic) structure of the unfolded protein would be inherently interesting. Unfortunately, the well established “wet chemistry” methods for protein synthesis are not suitable under the ultra high vacuum conditions necessary for the present study. New methods have to be developed that avoid additional reagents and polar solvents. Oxazolidine-2,5-diones have been shown to polymerize in solution[8] or even in the solid state[9,10] to form proteins when initiated with a base in a self-propagating chain reaction. Oxazoline diones can be prepared from various amino acids and phosgene[11] or the less hazardous triphosgene.[12] It should be possible to initiate the polymerization at the surface using the STM tip. Other protein precursors that can be initiated by heat or irradiation are salts of carboxy-hydroxamic acids[13,14] or substituted malonic acid mono azides.[15] Two different approaches will be pursued to prepare linear arrays of amino acid precursors [8] K. Heyns, R. Brockmann, Z. Naturforschg 1954, 9b, 21-26. [9] H. Kanazawa, Polymer 1992, 33, 2557-66. [10] B. M. Abo-El Khair, T. Komoto, T. Kawai, Makromol. Chem. 1976, 177, 2481-2489. [11] J. Grimshaw, S. D. Perera, J. Chem. Soc., Perkin Trans 2 1989, 1771-18. [12] I. A. Rivero, S. Heredia, A. Ochoa, Synth. Commun. 2001, 31, 2169-76. [13] C. D. Hurd, C. M. Buess, J. Am. Chem. Soc. 1951, 73, 2409. [14] C. D. Hurd, C. M. Buess, L. Bauer, J. Org. Chem. 1952, 17, 865. [15] T. Curtius, W. Sieber, Ber. Dtsch. Chem. Ges. 1922, 55, 1543. 31 (1.1) Unfolded protein on C60 meshes and wires C60 islands and stripes prepared by IP Berndt will be functionalized with lysine derivatives which subsequently will be polymerized to form unfolded protein chains. The amino acid lysine, therefore, will be converted to the corresponding oxazolidine-2,5- dione with triphosgene and the amino end group to an azide with azidotris(diethylamino)phosphonium bromide[16] or sodium azide and triflic anhydride.[17] The azide reacts with C60 by elimination[18] of N2 connecting the lysine side chain to C60. Polymerization will be initiated by irradiation or with the STM tip. Further substituted fullerenes will be synthesized by cyclopropanation of C60 using the Bingel-reaction with 2-bromoindan-1,3-dione. The C60 derivatives will be used by IP Ortega. (1.2) Unfolded “stretched protein“ We will prepare various oxazolidin-2,5-diones from amino acids, as well as carboxy-hydroxamic acids[19,20] and substituted malonic acid mono azides. IP Berndt will adsorb the “protein monomers” on metal sufaces and initiate the polymerizations using the STM tip, heat or light. Horn and Michel will characterize the electronic structure of these proteins. (2) Polydiacetylenes Self-assembled monolayers of diacetylenes polymerize upon irradiation or by application of an electric stimulus using a STM microprobe. The method can be used to create one-dimensional molecular nanowires[21] at desired positions with controlled termination by making artificial defects in the monolayer.[22] Applications range from sensors, non-linear optical materials to the realization of nanodevices.[23] The starting material will be synthesized by the IP5, Herges and the surface experiments are performed by IP Berndt. [16] S. P. Klump, H. Shechter, Tetrahedron Lett. 2002, 43, 8421-24. [17] C. J. Cavender, Shiner, V. J., J. Org. Chem. 1972, 37, 3567-69. [18] M. Prato, Q. Li, F. Wudl, V. Lucchini J. Am. Chem. Soc. 1993, 115, 1148. [19] C. D. Hurd, C. M. Buess, J. Am. Chem. Soc. 1951, 73, 2409. [20] C. D. Hurd, C. M. Buess, L. Bauer, J. Org. Chem. 1952, 17, 865. [21] M. kai-Kasaya, K. Shimizu, Y.Watanabe, A. Saito, M. Aono, Y. Kuwahara, Phys. Rev. Lett. 2003, 91(25) 255501/1255501/4. [22]Y. Okawa,. M. Aono, e-Journal of Surface Science and Nanotechnology (2004), 2 99-105. [23] H. Matsuda, H. Nakanishi, J. Mat. Chem. 2000, 10, 819-28 32 (3) Retinal adsoption on Au Switching processes of molecules at surfaces are of particular interest in view of the construction of nanodevices. Retinal is one of the biologically most important photoswitchable molecules. The cis-trans isomerization of retinal is the pivotal process for the visual perception and for the membrane transport in halophilic bacteria. To attach retinal to a gold surface the molecule has to be functionalized in such a way that the isomerization process is not hindered. There are several ways to attach a thiol or a dithiocarbamate group at the aldehyde function of Retinal. (a) Reaction of 2mercaptoethylamine with retinal, (b) functionalization of the surface with 2-mercaptoethylamine and addition of the retinal in a second independent step or (c) preparation of the imine with formaldehyde and simultaneous reaction with CS2 at the Au surface forming dithiocarbamate link. The surface chemisty will be performed in close collaboration with “IP6” (Gerber). The project will be started immediately after approval. For the time schedule and organization see d) Deliverables d) Deliverables/Milestones First year: report on the progress of the synthesis of the oxazolidine-2,5-diones from gylcine, alanine and cysteine and functionalization of lysine. First year: synthesis of diynes with a hydrocarbon backbone. First year: functionalization of retinal with 2-mercaptoethylamine Second year: synthesis of oxazolidine-2,5-diones from basic and acidic amino acids, such as aspartic acid, tryptophan and histidin and unnatural amino acids, such as D-alanine Second year: functionalization of retinal with formaldehyde, metalo-phthalocyanines as platforms. Third year: synthesis of molecular tripods for the attachment of retinal and other photoswitchable molecules. e) Justification for budget items The budget is mainly needed for the salary of a postdoc (36 months), chemicals, and equipment. For the photochemical polymerizations and the cis-trans isomerization of the surface bound retinal we need a tunable high-intensity light source e.g. the Model SID-201 from Photon Technology International. Standard equipment and the usual infrastructure (NMR, IR, UV, fluorescence MS etc.) for preparative chemistry is available in our institute. The travel budget should cover the expenses for mutual visits and for attending international meetings to present our results. . 33 Requested budget for IP5 – B3 Herges CRP Acronym: MOL-VIC IP Nr: must be consistent with the rules set by the relevant national funding agencies Rainer Herges, Unibersität Kiel Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS PI Name & Institution: Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short description/ justification of each budget item ** Salary position Ph.D. student Post-doc. Researcher 48.000 48.000 48.000 144.000 Design, synthesis and characterization of compounds High intensity light source SID-201, fiber optic coupler lamps , for photopolymerization and isomerization HPLC software and columns (accessories to existing instrument) senior researcher Technician student stipend / student assistant Equipment per item Item 1 21.000 21.000 Item 2 8.000 8.000 Item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs 4.000 5.000 5.000 14.000 10.000 12.000 10.000 32.000 including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 91.000 65.000 63.000 219.000 chemicals, glassware, analytics 34 IP5.– B3 RELATED PROJECTS HE 1530/11-1 „Synthese Möbius-aromatischer -Seite“ supported by the Deutsche Forschungsgemeinschaft. “Rational synthesis of carbon nanotubes”. We are aiming at the chemical synthesis of nanotubes with uniform geometries and thus well defined physical properties for the use in molecular electronics. “Design and synthesis of a light-driven proton pump”. Final goal is the uphill transport of protons through an artificial membrane or through a layer on a metal surface using photoswitchable molecules as carriers. Design and synthesis of “molecular plates and tripods” for the orthogonal orientation of photoswitchable molecules on Au surfaces. IP5. – B4 OTHER SCIENTIFIC COLLABORATIONS There is a close collaboration with the surface physicists Prof. Berndt and Prof. Magnussen in the Department of Physics of our University. We are preparing various photoswitchable molecules which are suitable for the preparation of functional surfaces. The monolayers are investigated using STM, AFM and electrochemistry. In collaboration with Prof. Faupel from Materials Department we are developing functional polymers. Properties such as shape, conductivity, and transparency can be reversibly switched. Prof. Kuzmany in Vienna and Prof. Thomsen (TU Berlin) are measuring Raman spectra of our nanotube structures. 35 IP6-B1 PI: Thomas Greber, University of Zürich (UZH) Endofullerene chains and switching isomers a) IP AIMS AND OBJECTIVES IP6 shall investigate molecular nano-structures, which spontaneously form on vicinal surface-templates. Besides stepped surfaces which provide 1D structures, we will also use kinked (chiral surfaces), which may pin single molecules on the kinks, i.e. form 0D structures and flat (111) surfaces, which provide 2D structures. We start with metal vicinal surfaces where we will profit from the knowledge of the whole MOL-VIC consortium on how to prepare them. In a second step, where functionality shall be demonstrated, it might become important to form structures in two steps, i.e. to pre-cover the metal substrate with molecules of type A, which will then allow to grow structures with molecules of type B on top of this less reactive and less metallic substrate. This has the purpose that molecules, as e.g. retinal will not lay flat on the surface and not loose their functionality as it is the conformational change (cis-trans isomerisation) upon light absorption. It has to be noted in brackets that UZH is currently investigating such a system, where hexagonal boron nitride layers play the role of molecules of type A (STREP Nanomesh). IP6 will investigate two types of self organized nano-structures on vicinal surfaces: Endofullerenes and cis-trans isomer reactions. A) Endofullerenes Molecular chain structures shall be built from endofullerenes. In this field N@C60 is a particularly interesting candidate. It is a unique molecule with one nitrogen atom enclosed in a cage of 60 carbon atoms. This conceptually simple atomic system has a 4S3/2 ground state with spin 3/2. The spin is chemically isolated from the surrounding and the molecule is thus considered as a candidate material for spintronic applications or quantum computers [Harneit, PRA, 65 (2002) 032322]. We would also like to use N@C60 as a “magnetic spy” on the surface. Therefore the behavior in its condensed form has to be studied. So far the molecules have been investigated with electron spin resonance in toluene solutions or in powder samples [Waiblinger et al. PRB, 64 (2001) 159901]. It has to be stressed that N@C60 chain formation is a very difficult task. This is mainly given by the fact that the nitrogen atoms tend to leave the carbon cage at about the same temperature as the C60 molecules evaporate. Furthermore, it is not clear whether N@C60 maintains its pure spin structure on a surface where the C60 cage is charged up by electron transfer from the substrate. Therefore this subproject will start with other endofullerenes as e.g. noble gas containing C60, which are known to be more stable and easier to handle. The production of endofullerenes strongly progressed recently [Komatsu et al. Science, 307 (2005) 238.] and we are confident to produce self-organized nanostructures from endofullerenes. 36 B) Switching Isomers Isomerisation changes the molecular conformation and is thus considered to become functional as a nanomechanical switch. This is e.g. beautifully realized in retinal, the molecule where the human perception process of light starts. There, an absorbed photon triggers the cis-trans isomerisation. We want to mimick this process at surfaces and form nano-structures from retinallike molecules which undergo conformational changes upon light absorption. We will consider two possible routes to form free-standing retinal molecules on surfaces: Either by substitution of the CHO-end group with e.g. a thiol group, or by the pre-coverage of the surface by a molecular carpet on which the original retinal molecules shall bind. This project will be in close collaboration with IP5 (Herges), which will provide the molecules and the chemical background. Furthermore it is related to IP4 (Horn) on stilben, which also undergoes isomerisation reactions. We expect that XPD experiments will demonstrate conformational changes as it occurs in an isomerisation reaction. Scheme of the isomerisation of retinal. Free standing retinal structures, bound with the CHO end to a surface shall be built and investigated with respect to switchability with light. The conformational changes will be monitored with XPD. Synergies: We expect from the existing CRP significant synergies with respect to the preparation of suitable molecules (Gourdon, Herges), techniques as low temperature scanning tunneling microscopy (Berndt), discussion and understanding of electronic effects as revealed by photoemission (Ortega, Horn, Michel) magnetism and chirality XRCD (Horn), and insight in functionalisation of such structures on the nanometer scale (theory in San Sebastian). IP6 will contribute precise XPD determinations of molecular conformations and their functionalisation change upon polymerization magnetization. IP6 will also supply on site support to all IP’s on MOL-VIC at the Swiss synchrotron Light Source. b) METHODOLOGY/EXPERIMENTS General: The Surface Physics Group of Prof. Dr. Jürg Osterwalder and Prof. Dr. Thomas Greber has a worldwide reputation in the field of photoemission spectroscopy, especially for new developments and its application to investigating structural, electronic and magnetic properties of surfaces. The laboratory features excellent experimental facilities, including a system that allows efficient preparation of surfaces and nanostructures and in-situ analysis by both STM and photoemission, a femtosecond laser system for time-resolved photoemission and electron diffraction experiments, as well as a spin-resolved photoemission experiment based at the nearby Swiss Light Source synchrotron radiation facility. The main expertise in the group is angle-resolved photoemission, and in particular photoelectron diffraction, holography, and Fermi surface mapping, as well as the preparation and characterization of atomic and molecular monolayers and of nanostructures based on vicinal crystal surfaces. It has the expertise and the equipment to contribute to the understanding of the atomic structure and self-assembly processes of molecules with up to 100 atoms on vicinal surfaces. 2π-X-ray photoelectron diffraction (XPD) is particularly well suited in order to directly determine the conformation of molecules at surfaces. 37 Related work on Self organized Nano-Structures at UZH: The system of one monolayer of C60 on vicinal Cu(665) is found to exhibit a one-dimensional molecular double chain structure, with a much stronger electron hopping rate parallel to the chains than perpendicular to the chains. STM picture from C60 molecular chains on a B-type Cu vicinal surface. Two chain types with two different contrasts and defect densities are seen. [Tamai et al. Surf. Sci. 566-568 (2004) 63] By means of X-ray photoelectron diffraction (XPD) it was demonstrated that the C60 molecules bind with two orientations, i.e. pentagon and hexagon bonds to the (111) terraces. Furthermore, the observed electron dispersion along the chains and the comparison with density functional theory (DFT) calculations emphasizes the two C60 orientations to constitute the two molecular chains. 2π-XPD maps from C60 on Cu(665). Top experiment, bottom Single Scattering Cluster (SSC) calculation with 50% pentagon and two equivalent hexagon orientations (each 25% weight). The agreement between experiment and theory is perfect. [Tamai et al. submitted] c) WORK PLAN The project will start after appointment with a qualified postdoc. The work will be organized according to the deliverables. d) DELIVERABLES/MILESTONES D6.1 month 12 IP6 reports on progress in preparation and characterization of low dimensional endofullerene structures on metallic surfaces. D6.2 month 12 IP6 reports on progress in preparation and characterization of low dimensional retinal structures on metallic surfaces. D6.3 month 24 IP6 reports on N@C60 endofullerene structures on surfaces and 38 whether the spin on the N atoms may be detected. D6.4 month 24 IP6 reports on retinal structures on surfaces and whether the molecules may be switched by light. D6.5 month 36 IP6 reports on the whole project. e) JUSTIFICATION OF BUDGET The budget mainly consists in salaries, running costs for the experiment, travel and publication money. We ask for salaries of a postdoc (36 month) and a technician (6 month) and for the expenses of a guest professor (5 month). The postdoc position is necessary in order to run the above mentioned XPD experiment at the Swiss Light Source, and to train students on the PhD and the graduate level. The technician position is necessary in order to further develop the difficult task to evaporate large molecules of which nanogram quantities were available, only. The money for a guest is important in order to fertilize the research, in particular in view of the theoretical understanding of the results. We furthermore expect from this guest to help to maximize synergies inside and outside MOL-VIC and to develop new opportunities and views in the field of self organized nano-structures. The surface physics group at UZH will contribute the salary of the PI, who will work about 30% on MOL-VIC, and potential PhD students on the project. A contribution to the running costs for the experiments is expected. E.g. the consumable “channeltrons” has to be covered from inside MOL-VIC. The surface physics group of Prof. Dr. Jürg Osterwalder and the physics institute at UZH will add about an equal amount to the running costs and the infrastructure of IP6. Travel and publication money is important for the networking inside MOL-VIC and the dissemination of the results to the world-wide community. Again, the outside contribution from the surface physics group and the physics institute at UZH will be about an equal amount to travel and publication money of IP6. . 39 Overall budget of the CRP (A9 f): CRP Acronym: MOL-VIC IP Nr:6 Funding Agency solicited: Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies PI Name & Institution: GREBER, UZH Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short description/ justification of each budget item ** Salary position Ph.D. student Post-doc. Researcher 36/1 senior researcher 5/13 Technician 6/6 79’584 16’123 79’584 20’000 16’123 79’584 238’753 20’000 32’246 Guest Professor 6’000 Evaporator components Runs the Project at the Synchrotron Technician for special evaporator development student stipend / student assistant Equipment per item Item 1 6’000 Item 2 Item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) 2’100 2’100 2’100 6’300 7’000 500 5’000 8’000 1’000 8’000 1’500 5’000 23’000 3’000 21’061 27’561 18’237 66’860 500 500 1’000 2’000 Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 126’866 165’868 110’423 403’159 Channeltrons 40 IP6 – B3 RELATED PROJECTS Author SNF und PSI “Direct determination of adsorption induced structural changes in large molecules by Near Node Photoelectron Holography” (0.1 MEuro/2 years) ends 2006. Coauthor CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces” (0.03 MEuro/5 years) ends 2006. Coauthor of the SNF fundings of the group of J. Osterwalder 2005 (0.5 Meuro/2 years), ends 2007. Coauthor of STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional Surfaces” (2 MEuro/3 years) ends 2008. SNF Swiss National Science Fundation PSI Paul Scherrer Institut IP6 – B4 OTHER SCIENTIFIC COLLABORATIONS Ari Seitsonen, Paris, DFT Theory, ZX Shen, Stanford, Photoemission, Wolfgang Harneit, FU Berlin, Endofullerenes, Koichi Komatsu, Kyoto, Endofullerenes, Abdelkader Kara, Manhattan, DFT Theory, CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces”: Herbert Over, Giessen, STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional Surfaces”: Herrmann Sachdev, Saarbrücken, precursor molecules Matthias Schreck, Würzburg, crystalline thin film samples Neil Campness, Nottingham, large molecules synthesis Peter Beton Nottingham, large molecules, STM Herbert Over, Giessen, LEED Peter Blahe, Wien, DFT theory Joost Frenken, Leiden, High temperature STM David Williams, Hitachi Cambridge, Nanotechnolgy. 41 Section C - Associated Project (AP) AP1-C1 PI: André Gourdon, CEMES-CNRS, Toulouse 1 Associated Project aims & objectives "AP1 Gourdon" general objective is to provide dedicated new molecules or molecular systems to understand the 1D supramolecular organisation on vicinal surfaces. 2 Methodologies/experiments The supramolecular organisation of molecules on a surface is function of a subtle balance of various parameters such as the molecule-substrate Van der Waals forces, the molecular rigidity towards these forces, the inter-molecular interactions (through space or mediated by the substrate), the chemical reactivity, the mobility on the surface, etc.. Therefore molecules design will be adapted in function of the first results obtained on the benzodiguanamie and the pyrazolecarboxylic molecules in the project first year. 3 Work plan Two of the main problems encountered in the study of supramolecular ordering of somehow fragile large organic molecules on a substrate are 1) the difficulty to transfer the molecule to the substrate by sublimation in UHV 2) the lack of mobility of the molecules at rather low temperature which prevents a clean 2D "recrystallisation" to give well ordered structures. In order to improve the mobility of the molecule at not-too high temperatures, and to reduce the sublimation point of large aromatic molecules, it is necessary to equip these molecules with bulky substituants which reduces the intermolecular interactions in the solid state and the aromatic part-substrate interaction (and then the annealing temperature) after transfer on a clean metallic surface. We have recently shown that molecules of the type: Hexa-tertButylphenylbenzene allow nice supramolecular ordering on Cu(111) (Phys. Rev. B (2005) B71, 165428.). We propose to extend this type of structure to functionalized molecules able to show 1D ordering from a general structure of tetra-tertButyl-(functionalised)diaromatic-benzene 1. A first synthetic target will be the dipyridyl tertar-tert-butylbenzene 2 using synthetic methodologies we have just developed. It should give interesting 1D structures by coadsorption with organic diacids like terephthalic acid. R X X R 1 N N 2 The next synthetic objectives will be to add various X-R fragments to this design to increase the intermolecular interactions eventually by co-adsorption experiments for instance with 4 + 5. 42 H2N N N NH2 N N N N N N H2N NH2 4 3 O OH HO O 5 Depending on the observation done by the project partners, new molecules will be proposed used the synthetic methodology that will be developed for molecules 2 to 5 4 Deliverables and/or milestones See work plan AP1-C2 - Information on funding No specific external funding; the expenses will be paid by the group budget. 43 Annexes to the Proposal MOL-VIC IP1.- ANNEX I----------- CV ORTEGA Birth date: 7th January, 1963 in San Sebastián (Spain). Address: Dept. Física Aplicada I, Universidad del País Vasco, Plaza de Oñate 2, 20018-San Sebastián. Phone number: +34 943 018289; e-mail: ortega@sq.ehu.es UNIVERSITY EDUCATION: Bachelor in Physical Sciences, Universidad Autonoma de Madrid, June 1986. Ph.D., Universidad Autonoma de Madrid, September 1990. EMPLOYMENT RECORD: Researcher as graduate student at Univ. Autonoma de Madrid (1986 - 1990). Full-time Associate Professor at Univ. Autonoma de Madrid (1990-1991). Post-doc at the IBM T. J. Watson Research Center, New York (USA) (1991-1993). Researcher at Univ. Autonoma de Madrid (1993-1995). Visiting professor Univ. del País Vasco San Sebastián (1995 - 1996). Full-time Associate Professor at Univ. del País Vasco San Sebastián (1996 - 1998). Full Assistant Professor at Univ. del País Vasco San Sebastián since 1998. Full Professor at Univ. del País Vasco San Sebastián since 2003. RESEARCH: Areas of research include: epitaxial growth of metal on metal, electronic structure of metallic interfaces, electronic and geometric structure of metal-semiconductor interfaces, nanotechnology and nanofabrication, electronic and geometric structure thin films, vicinal surfaces and lateral nanostructures. Experimental Techniques used: Inverse Photoemission Spectroscopy (IPS), Photoemission with synchrotron radiation, comprising Ultraviolet Photoemission Spectroscopy (UPS) (both angle-integrated and angle-resolved) and X-Ray Photoemission Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Low Energy Electron Diffraction (LEED), Scanning Tunneling Microscopy (STM). PUBLICATIONS: About 75 articles in refereed international journal. The 10 most relevant for this proposal are the following 1. "Magnetic Nanostructures", F. J. Himpsel, J. E. Ortega, G. J. Mankey, and R. F. Willis, Advances in Phys. 47, 511 (1998). (Review article) 2. “The electron wave function at a vicinal surface: Switch from terrace to step modulation”, J. E. Ortega, S. Speller, A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio, and F. J. Himpsel, Phys. Rev. Lett. 84, 6110 (2000). 3. “One-dimensional Ag-Cu superlattices on vicinal Cu(111)”, A. R. Bachmann, A. Mugarza, S. Speller, and J. E. Ortega, Phys. Rev. B 64, 153409 (2001). 4. “Electron confinement in Surface States on a Stepped Gold Surface Revealed by Angle-Resolved Photoemission”, A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de Abajo, and J. E. Ortega, Phys. Rev. Lett 87, 107601 (2001). 5. “Ag-induced zero- and one-dimensional nanostructures on vicinal Si(111), J. Kuntze, A. Mugarza, y J. E. Ortega, Appl. Phys. Lett. 81, 2463 (2002). 6. “Driving forces for Ag-induced nanostructuration on vicinal Cu(111)”, A. R. Bachmann, S. Speller, A. Mugarza, and J. E. Ortega, Surf. Sci. 526, L143 (2003). 7. “Electronic States at Vicinal Surfaces”, A. Mugarza y J. E. Ortega, J. Phys. Cond. Mat. 15, S3281 (2003). 8. “Tuning surface state dimensionality in Cu nanostripes”, J. Lobo, E. G. Michel, A. Bachmann, S. Speller, J. Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602 (2004). 9. “Fermi gap stabilization of an incommensurate two-dimensional superstructure”, F. Schiller, J. Cordón, D. Vyalikh, A. Rubio, and J. E. Ortega, Phys. Rev. Lett. 94, 016103 (2005). 10. “Scattering of surface states at step edges in nanostripe arrays”, F. Schiller, J. Cordón, M. Ruiz-Osés, and J. E. Ortega, Phys. Rev. Lett 95, 066805 (2005). MOL-VIC IP2.- ANNEX I----------- CV BERNDT 1962 1982-1984 1984-1987 1985-1987 1987-1988 1988-1992 18.2.1992 1992-1996 1996-1999 Aug. 1996 Jul. 1999 Oct. 2000 28.3.2001 Mar. 2002 22.11.2003 Born in Gladbeck, Germany Student of physics and ''Vordiplom'' at the University of Osnabrück Student of physics at the University of Göttingen, Germany Diploma project at the Max-Planck-Institut für Strömungsforschung in Göttingen with Prof. J.P. Toennies on surface phonons. Scientist at the Max-Planck-Institut für Strömungsforschung. Scientist with the IBM Research Division, Zurich Research Laboratory in Rüeschlikon, Switzerland Awarded PhD summa cum laude from the University of Basel. Supervisors: Prof. H.-J. Güntherodt and Dr. H. Rohrer. “Premier assistant'' at the Institut de Physique Expérimentale of the University of Lausanne with Prof. W.-D. Schneider Associate professor at the RWTH Aachen, Germany Visiting scientist at the National Research Institute for Metals, Tsukuba, Japan Full professor at the University of Kiel, Germany Managing Director of the IEAP Received Nanoscience Price 2001” ”professeur invité'' at the Université Paul Sabatier, Toulouse Received Joachim Jungius-Price Selected publications: [1] J. Kuntze, R. Berndt, P. Jiang, H. Tang, A. Gourdon, C. Joachim, Conformations of a molecular wire adsorbed on a metal surface, Phys. Rev B 65, 233405 (2002) [2] G. Hoffmann, L. Libioulle, R. Berndt, Tunneling induced luminescence from adsorbed organic molecules with submolecular lateral resolution, Phys. Rev. B 65, 212107 (2002) [3] G. Hoffmann, R. Berndt, P. Johansson, Two-Electron Photon Emission from Metallic Quantum Wells, Phys. Rev. Lett. 90, 046803 (2003) [4] L. Limot, T. Maroutian, P. Johansson, R. Berndt, Surface State Stark Shift in a Scanning Tunneling Microscope, Phys. Rev. Lett. 91, 196801 (2003) [5] J. Kuntze, X. Ge, R. Berndt, Chiral structures of lander molecules on Cu(100), Nanotechnology 15, S337-S340 (2004) [6] G. Hoffmann, Th. Maroutian, R. Berndt, Color View of Atomic Highs and Lows in Tunneling Induced Light Emission, Phys. Rev. Lett. 93, 076102 (2004) [7] L. Limot, E. Pehlke, J. Kröger, R. Berndt, Surface-State Localization at Adatoms, Phys. Rev. Lett. 94, 036805 (2005) [8] L. Limot, J. Kröger, R. Berndt, A. Garcia-Lekue, W.A. Hofer, Atom Transfer and Single-Adatom Contacts, Phys. Rev. Lett. 94, 126102 (2005) [9] N. Néel, J. Kröger, R. Berndt, Highly Periodic Fullerene Nanomesh, subm. to Advanced Materials [10] J. Kröger, H. Jensen, R. Berndt, R. Rurali, N. Lorente, Molecular Orbital Shift of Perylenetetracarboxylic-Dianhydride, subm. to Phys. Rev. Lett., see also cond-mat/0506025. MOL-VIC IP3.- ANNEX I----------- CV MICHEL Birth date: 3rd May, 1962 in Madrid (Spain). Address: Dept. de Física Materia Condensada, Universidad Autónoma de Madrid, 28049-Madrid. Phone number: +34 91 397 4759; e-mail: enrique.garcia.michel@uam.es UNIVERSITY EDUCATION: Bachelor in Physical Sciences, Universidad Autónoma de Madrid, June 1985. M.Sc. (Surface Physics), Universidad Autónoma de Madrid, June 1986. Ph.D., Universidad Autónoma de Madrid, October 1988. Faculty prize for best thesis. EMPLOYMENT RECORD: Researcher as graduate student at Univ. Autónoma de Madrid (1986 - 1988). Researcher at the Fritz Haber Institut of the MPG in Berlin (September 1987 - December 1987). Full-time Associate Professor at Univ. Autónoma de Madrid (1988 until February 1997). Researcher at the Hamburg Synchrotron Radiation Laboratory (HASYLAB) (1989 - 1990). Research Fellow of the Alexander von Humboldt Foundation (Germany) (1990). Full Professor at the Universidad Autónoma de Madrid (February 1997 until now). Director of the Department of Condensed Matter Physics (since March 2005). RESEARCH: My areas of research have include: epitaxial growth of metal on metal, electronic structure of metallic interfaces, electronic and crystallographic structure of metal-semiconductor interfaces, electronic Structure of High-Tc superconductors, nanotechnology and nanofabrication, electronic and crystallographic structure of halogensemiconductor interfaces, epitaxial growth of silicides on silicon, surface phase transitions, surface charge density waves, electronic confinement at surfaces. Experimental Techniques used: Inverse Photoemission Spectroscopy (IPS), Ultraviolet Photoemission Spectroscopy (UPS) (both angle-integrated and angle-resolved), X-Ray Photoemission Spectroscopy (XPS), Ion Scattering Spectroscopy (ISS), Auger Electron Spectroscopy (AES), Thermal Desorption Spectroscopy (TDS), Low Energy Electron Diffraction (LEED), Surface X-ray diffraction (SXRD), Scanning Tunneling Microscopy (STM), Near-Edge X-ray Extended Fine Structure (NEXAFS), Photoemission of Adsorbed Xenon (PAX), X-Ray Photoelectron and Auger Electron Diffraction (XPD, AED), X-Ray Standing Waves (XSW), X-Ray Fluorescence with Synchrotron Radiation. I have supervised six PhD thesis, two other are to be finished in 2006, plus many Diploma Thesis. PUBLICATIONS: I have published approx. 100 articles in refereed international journal. The 10 most relevant papers from last 5 years are listed in Annex 2. OTHER R+D ACTIVITIES I have served in several international and national editorial and evaluation committees as: International Programme Committee of synchrotron LURE in Orsay (France), since 1991. Spanish delegate in the Scientific Committee of the European synchrotron ESRF (1993-94) and Scientific activity evaluator for the beamline BL32 of ESRF (1999). Spanish delegate in the EU panel “New applications of accelerators: free electron laser” (1994-95) and expert in the EU Growth Programme (2000) Editor of “Journal of Physics Condensed Matter” (since 2000) and Chairman of the Surface Science Editorial Board (since January 2005). Fellow of the Institute of Physics (London). Programme Committee of SLS (Swiss Light Source) of the PSI (Switzerland), since January 2002 I have organized several scientific meetings, the most important being the 19th European Conference on Surface Science, held in Madrid in September 2000 (700 participants). I am referee of many scientific journals and regularly participate in the evaluation of scientific and technological grants at national and international level. MOL-VIC IP3.- ANNEX I----------- CV HORN December 17th, 1946 Date of birth. Parents: Kurt Horn, accountant, and Erika Horn 1953 -1966 Primary and secondary school in Düsseldorf, Germany 1966 -1968 Military service in Borken/West Germany. Final rank: Second Lieutenant 1968 -1973 Undergraduate education in physics at Rheinisch-Westfälische Technische Hochschule Aachen. Diploma thesis (with Prof. H.Ibach ) on "Oxidation of Si(111) single crystal surfaces" 1973 - 1976 Graduate studies at Queen Mary College, University of London, Great Britain, with Prof, J.Pritchard. Ph.D. thesis: "A study of adsorption on metal single crystals by IR absorption spectroscopy" June 1976 Awarded degree of Doctor of Philosophy (University of London) August 1976 Post-doctoral position at the Fritz-Haber-Institut of the Max-PlanckGesellschaft, with Prof. A.M.Bradshaw. First work in photoelectron spectroscopy. from 1978 onwards Staff scientist at the Fritz-Haber-Institut, with an independent research group 1979 and 1981 work at University of Wisconsin Synchrotron Radiation Center, with Prof. E.W.Plummer, Univ. of Pennsylvania, and Dr.D.E.Eastman, IBM Research 1984 named "Privatdozent" in the Freie Universität Berlin from 1992 Editor of "Handbook of Surfaces Vol. II - Electronic Structure" with Prof. Matthias Scheffler 1993 Chairman of Symposium "Electronic Structure of Surfaces", with Prof. Matthias Scheffler 1995 awarded the rank of Adjunct Professor in the Department of Physics of the Freie Universität Berlin 1997 elected Fellow of the American Vacuum Society 1998 .... Chairman of Proposal Review Committee of the ELETTRA Synchrotron radiation facility in Trieste, Italy 2000 Co-Organizer of a Symposium on Surface and Thin Films at the MRS Fall Meeting in Boston, Mass. (USA) Author and co-author of about 165 papers in refereed scientific journals Adviser for about 20 Ph.D. and Diploma students Frequent teaching assignments at the Freie Universität Berlin Member of Deutsche Physikalische Gesellschaft, European Physical Society, Member of the American Vacuum Society. Frequent activities as External Referee for Ph.D. theses, proposals and vacant positions in research institutes and departments both in Germany and abroad MOL-VIC IP5.- ANNEX I----------- CV HERGES Study Oct.1975 - March 1981, Study of chemistry at the University of the Saarland, Saarbrücken (a city close to the French border) - 10 Semester. Diplom March 1981, Saarbrücken Diplom thesis Title: "Valence Isiomerisation and Ring inversion of Cycloheptatrienenes" with Prof. Dr. H. Dürr. Graduation July 1981 - July 1984; Scholarship of the "Fonds der Chemischen Industrie"; Department of Organic Chemistry Technical University Munich. Title: "Computer Aided, Deductive Search for Novel Reactions and their Experimental Verification" with Prof. I. Ugi. Post-Doc. Sept. 1984 - Sept. 1985; Feodor-Lynen-Scholarship of Alexander von Humboldt-Stiftung; University of Southern California, Los Angeles with Prof. G. A. Olah. Synthesis of Carbocations and Dications. Habilitation Dec. 1985 - July 1992; Liebig-Scholarship of the Fonds der Chemischen Industrie; Institute f. Organic Chemistry, Universität Erlangen-Nürnberg with Prof. P. v. R. Schleyer. Title: "Reaction Planning: Rational Planning of Chemical Reactions". Visiting Prof. 15. Sept -15. Okt. 1995 at the École Normale Supérieure, Paris. Professor (C3) since 1. Feb. 1996, Institut für Organische Chemie, Technische Universität Braunschweig. Visiting Prof. Okt. 1998 - Dez. 1998 at the Stanford University. Professor (C4) since 1. March 2001, Institut für Organische Chemie, Christian-Albrechts-Universität Kiel. Awards Dissertation Award of the Technical Universitiy Munich, July 1986 Chemical Structure Association Trust Award 1993 Habilitation Award: ADUC Jahrespreis für Habilitanden 1993 Fields of Research Synthetic Chemistry Quantum Chemistry Computational Chemistry MOL-VIC IP6.- ANNEX I----------- CV GREBER Born on February 23rd 1960 in Solothurn, Switzerland. Son of Hedwig Maria Greber - Renggli and Josef Alois Greber. Single, no children. Finals: 1966-1979 School in Zofingen up to Matura (Typus C). 1980-1986 Studies on Physics at ETH Zürich. 1986 Diploma "Wasser auf Cer", in the group of Prof. Dr. H.-C. Siegmann with Dr. L. Schlapbach. 1990 Promotion " Two aspects concerning 4f impurities on metals", ETH Diss No 9092 in Zürich and Fribourg with Prof. Dr. H.-C. Siegmann and Prof. Dr. L. Schlapbach. 1997 Habilitation "Charge-transfer induced particle emission in gas surface reactions", Universität Zürich. Jobs: 1986-1988 Assistant in the Laboratorium für Festkörperphysik at ETHZ. 1988-1991 Assistant at the Université de Fribourg, Schweiz. 1990 Guest at the Universiity of Kogaquin, Tokyo, with Prof. Dr. S. Suda. 1991-1994 Postdoc at the Fritz-Haber-Institute, Berlin, with Prof. Dr. G. Ertl with scholarships from the Schweizerischen Nationalfonds and the Alexander von Humboldt Stiftung. Work on "Electron emission in nonadiabatic gas surface reactions". since 1995 Oberassistant in the group of Prof. Dr. J. Osterwalder at the Universität Zürich. Set up of a new surface physics lab. Teaching courses: Surface Physics, Electron Spectroscopy, Math. Methods in Physics, Solid State Physics, Nano- and Interface Physics. 1997 Guest of Prof. Dr. U. Heinzmann at ZIF Bielefeld within the "Interactions of oriented molecules" project. 1997 Privatdozent (PD)/Oberass. habil. mbA. 2000 Referee in the program committee “surfaces” of LURE. Awards: 1991 "SPG Preis gestiftet von der Firma IBM für hervorragende Arbeiten auf dem Gebiet der kondensierten Materie 1991" with A. Stuck and Dr. J. Osterwalder . 2004 Titularprofessor Own projects: 1997,2004 "Near Node Photoelectron Holography", SNF. 1997 Collaboration in the Advanced Photoemission Experiment (APE) at the Synchrotrone Trieste (ELETTRA). 2000 “Time-resolved low energy electron diffraction from large molecules on surfaces”, SNF, DFG, CERC3. MOL-VIC AP1.- ANNEX I----------- CV GOURDON Dr. André Gourdon is Research Director at CNRS. After a post-doc in 1980-1981 at the Inorganic Chemistry Laboratory (Oxford) in the group of Prof. M. L. H Green, he joined the CNRS (Paris, Université P. & M. Curie) in 1981 to work on organometallic chemistry and crystallography of iron clusters as models of metallic nanoparticules. He joined Prof. J.-P. Launay's Molecular Electronics group in 1988 to study intramolecular electron transfer and moved with his group to Toulouse in 1990. Dr Gourdon is interested in the design, synthesis and structural studies of organic and inorganic molecular devices for nanoscience and molecular electronics. Groupe Electronique Moléculaire, CEMES-CNRS, 29, Rue J. Marvig BP 4347, 31055 Toulouse Cedex, France, Phone: (33) 562 25 78 59; Fax: (33) 562 25 79 99, Email: gourdon@cemes.fr Selected recent publications Synthesis of Molecular Landers André Gourdon EurJOC (1998) 2797-2801. Conformational Changes of Single Molecules Induced by Scanning Tunneling Microscopy Manipulation: A Route to Molecular Switching F. Moresco, G. Meyer, K.-H. Rieder, H. Tang, A. Gourdon and C. Joachim Phys. Rev. Letters (2001) 86:4, 672-675. Low temperature manipulation of big molecules in a constant height mode F. Moresco, G. Meyer, K.H. Rieder, H. Tang, A. Gourdon et C. Joachim Applied Physics Letter (2001) 78, 306-308. Recording Intramolecular Mechanics during the Manipulation of a Large F. Moresco, G. Meyer, K. H. Rieder, H. Tang, A. Gourdon and C. Joachim Phys. Rev. Letters (2001) 87, 088302 Molecule Conformations of a long molecular wire with legs on a Cu(100) surface T. Zambelli, H. Tang; J. Lagoute, S. Gauthier, A. Gourdon and C. Joachim Chem. Phys. Letters (2001) 348, 1-6 Conformations of a molecular wire adsorbed on a metal surface J. Kuntze, R. Berndt, J. Ping, H. Tang, A. Gourdon and C. Joachim Phys. Rev. B (2002), 233405, 1-4 Organic molecules acting as templates on metal surfaces F. Rosei, M. Schunack, P. Jiang, A. Gourdon, E. Laegsgaard, I. Stensgaard, C. Joachim and F. Besenbacher Science (2002), 296:5566, 328-331. Probing the Different Stages in Contacting a Single Molecular Wire Francesca Moresco, Leo Gross, Micol Alemani, Karl-Heinz Rieder, Hao Tang, André Gourdon, and Christian Joachim Phys. Rev. Lett. 91, 036601 (2003) Molecules on Insulating Films: Scanning-Tunneling Microscopy Imaging of Individual Molecular Orbitals Jascha Repp, Gerhard Meyer, Sladjana M. Stojkovi , André Gourdon, and Christian Joachim Phys. Rev. Lett. 94, 026803 (2005). MOL-VIC IP1.-ORTEGA ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) 1. “The electron wave function at a vicinal surface: Switch from terrace to step modulation”, J. E. Ortega, S. Speller, A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio, and F. J. Himpsel, Phys. Rev. Lett. 84, 6110 (2000). 2. “One-dimensional Ag-Cu superlattices on vicinal Cu(111)”, A. R. Bachmann, A. Mugarza, S. Speller, and J. E. Ortega, Phys. Rev. B 64, 153409 (2001). 3. “Electron confinement in Surface States on a Stepped Gold Surface Revealed by Angle-Resolved Photoemission”, A. Mugarza, A. Mascaraque, V. Pérez-Dieste, V. Repain, S. Rousset, F. J. García de Abajo, and J. E. Ortega, Phys. Rev. Lett 87, 107601 (2001). 4. “Ag-induced zero- and one-dimensional nanostructures on vicinal Si(111)”, J. Kuntze, A. Mugarza, and J. E. Ortega, Appl. Phys. Lett. 81, 2463 (2002). 5. “Driving forces for Ag-induced nanostructuration on vicinal Cu(111)”, A. R. Bachmann, S. Speller, A. Mugarza, and J. E. Ortega, Surf. Sci. 526, L143 (2003). 6. “Measurement of electron wave functions and confining potentials via photoemission”, A. Mugarza, J. E. Ortega , F. J. Himpsel, and F. J. García de Abajo, Phys. Rev. B 67, 081404 (2003) 7. “Tuning surface state dimensionality in Cu nanostripes”, J. Lobo, E. G. Michel, A. Bachmann, S. Speller, J. Kuntze, and J. E. Ortega, Phys. Rev. Lett. 93, 137602 (2004). 8. “Fermi gap stabilization of an incommensurate two-dimensional superstructure”, F. Schiller, J. Cordón, D. Vyalikh, A. Rubio, and J. E. Ortega, Phys. Rev. Lett. 94, 016103 (2005). 9. “Scattering of surface states at step edges in nanostripe arrays”, F. Schiller, J. Cordón, M. Ruiz-Osés, and J. E. Ortega, Phys. Rev. Lett 95, 066805 (2005). 10. “Surface state scattering at a buried interface”, F. Schiller, R. Keyling, E. V. Chulkov, and J. E. Ortega, Phys. Rev. Lett. 95, 126402 (2005). MOL-VIC IP2.-BERNDT ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) J. Kuntze, X. Ge, R. Berndt, Chiral structures of lander molecules on Cu(100), Nanotechnology 15, S337 (2004) L. Limot, E. Pehlke, J. Kröger, R. Berndt, Surface-State Localization at Adatoms, Phys. Rev. Lett. 94, 036805 (2005). L. Limot, J. Kröger, R. Berndt, A. Garcia-Lekue, W. A. Hofer, Atom Transfer and Single-Adatom Contacts, Phys. Rev. Lett. 94, 126102 (2005). N. Neel, J. Kröger, R. Berndt, Highly Periodic Fullerene Nanomesh, Advanced Materials (in press) J. Kröger, H. Jensen, R. Berndt, R. Rurali, N. Lorente, Molecular Orbital Shift of PerylenetetracarboxylicDianhydride, submitted to Phys. Rev. Lett. IP3.-MICHEL ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) 1-“The electron wave function at a vicinal surface: Switch from terrace to step modulation” J. E. Ortega, S. Speller, A. Bachmann, A. Mascaraque, E. G. Michel, A. Mugarza, A. Närmann, A. Rubio, and F. J. Himpsel. Physical Review Letters 84 (2000) 6110. 2-“Periodicity and thickness effects in the cross section of quantum well states” A. Mugarza, J.E. Ortega, A. Mascaraque, E.G. Michel, K.N. Altmann, and F.J. Himpsel Physical Review B 62 (2000) 12672. 3-“Reversible structural phase transitions in semiconductor and metal/semiconductor surfaces” A. Mascaraque and E.G. Michel Journal of Physics: Condensed Matter 14, 6005 (2002). 4- “Phonon Softening, Chaotic Motion, and Order-Disorder Transition in Sn/Ge(111)'' D. Farías, W. Kaminski, J. Lobo, J. Ortega, E. Hulpke, R. Pérez, F. Flores, and E.G. Michel Physical Review Letters 91 (2003) 016103. 5-“Electronic structure of Sn/Si(111)-(p3 £ p3)R30± as a function of Sn coverage” J. Lobo, A. Tejeda, A. Mugarza, and E.G. Michel Physical Review B 68, 235332 (2003). 6-“Tuning surface state dimensionality in Cu nanostripes” J. Lobo, E.G. Michel, A.R. Bachmann, S. Speller, J. Kuntze, and J.E. Ortega Physical Review Letters 93 (2004) 137602. 7-“Photoelectron diffraction study of the Si-rich 3C-SiC(001)-(3 £ 2) structure” A. Tejeda, D. Dunham, F.J. García de Abajo, J.D. Denlinger, E. Rotenberg, E.G. Michel, and P. Soukiassian Physical Review B 70, 045317 (2004). 8-“Accurate band mapping via photoemission from thin films” A. Mugarza, A. Marini, T. Strasser, W. Schattke, A. Rubio, F. J. García de Abajo, J. Lobo, E. G. Michel, J. Kuntze, and J. E. Ortega Physical Review B 69, 115422 (2004). 9-“Structural phase transitions in two-dimensional systems: Pb/Ge(111) and Sn/Ge(111)” A. Cano, A.P. Levanyuk, and E.G. Michel Zeitschrift für Kristallographie 220 (2005) 663. 10-“Fermi surface gapping and nesting in the surface phase transition of Sn/Cu(100)” J. Martínez-Blanco, V. Joco, H. Ascolani, A. Tejeda, C. Quirós, G. Panaccione, T. Balasubramanian, P. Segovia, and E.G. Michel Physical Review B 72 (2005) 041401(R) MOL-VIC IP4.-HORN ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) 1. S.R.Barman, P.Häberle, K.Horn, J.Maytorena und A.Liebsch Quantum well behavior without confining barrier observed via dynamically screened photon field Phys.Rev. Lett. 86, 5108 (2001). 2. L. Aballe, C. Rogero, S. Gokhale, S. Kulkarni und K. Horn Quantum-well states in ultrathin aluminium films on Si(111) Surface Science 482 - 485, 488(2001). 3. M.P.Casaletto, R.Zanoni, M.Carbone, M.N.Piancastelli, K.Weiss, L.Aballe, und K.Horn Methanol adsorption on Si(100)-(2 x 1) investigated by high resolution photoemission Surface Science 505, 251(2002) 4. L.Aballe, C.Rogero, und K.Horn Quantum well states in Mg films on Si(111) Phys.Rev. B 65, 125319 (2002) 5. J.Schaefer, S.C.Erwin, M.Hansmann, Z.Song, E.Rotenberg, S.D.Kevan, C.S.Hellberg, und K.Horn Random Registry shifts in Quasi-one-dimensional Adsorbate Systems Phys.Rev. B 67, 085411(2003). 6. J.H. Dil, J.W. Kim, S. Gokhale, M. Tallarida and K. Horn Self-organization of Pb thin films on Cu(111) induced by quantum size effects: An angle-resolved photoemission study Phys.Rev. B70, 045405 (2004). 7. J. I. Pascual, G. Bihlmayer, Yu.M. Koroteev, H.-P. Rust, G. Ceballos, M. Hansmann, K. Horn, E.V. Chulkov, S. Blügel, P.M. Echenique, and Ph. Hofmann Role of Spin in quasiparticle interference Phys.Rev.Lett. 93, 196802(2004). 8. J. W. Kim, M. Carbone, J. H. Dil, M. Tallarida, R. Flammini, M. P. Casaletto, K. Horn, and M. N. Piancastelli Atom-specific identification of adsorbed chiral molecules by photoemission Phys.Rev.Lett. 95, 107601 (2005). MOL-VIC IP5.-HERGES ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) Delocalization of Electrons in Molecules R. Herges, D. Geuenich J. Phys. Chem. A 2001, 105, 3214-3220 Homoaromaticity in tris(ethylene)nickel(0) and tris(ethyne)nickel(0) R. Herges, A. Papafilippoulos Angew. Chem. 2001, 113, 4809-4813 Angew. Chem. Int. Ed. Engl. 2001, 40, 4671-4674 Two Unusual, Competitive Mechanisms for (2-Ethynylphenyl)triazene Cyclization; Pseudocoarctate versus Pericyclic Reactivity D. B. Kimball, R. Herges, M. M. Haley, J. Am. Chem. Soc. 2002, 124, 1572-1573 Diciphering the Mechanistic Dichotomy in the Cyclization of 1-(2-Ethynylphenyl)-3,3-dialkyltriazenes: Competition Between Pericyclic and Pseudocoarctate Pathways. B. Kimball, T. J. R. Weakley, R. Herges, M. M. Haley J. Am. Chem. Soc. 2002, 124, 13463-13473 Synthesis of a Chiral Tube R. Herges, M. Deichmann, T. Wakita, Y. Okamoto Angew. Chem. 2003, 115, 1202-1204. Angew. Chem. Int. Ed. Engl. 2003, 42, 1170-1172. Picotube Tetraanion: a Novel Lithiated Tubular System N. Treidel, M. Deichmann, T. Sternfeld, T. Sheradsky, R. Herges, M. Rabinowitz Angew. Chem. 2003, 115, 1204-1208. Angew. Chem. Int. Ed. Engl. 2003, 42, 1172-1176 Synthesis, Structure and Complexation Properties of Amide Substituted Norbornadiene and Quadricyclane Derivatives T. Winkler, Ina Dix, P. G. Jones, R. Herges Angew. Chem. 2003, 115, 3665-3668. Angew. Chem. Int. Ed. Engl. 2003, 42, 3541-3544 Synthesis of a Möbius aromatic hydrocarbon D. Ajami, O. Oeckler, A. Simon, R. Herges Nature 2003, 426, 819-821. Arsenic- Interactions Stabilize a Self-Assembled As2L3 Supramolecular Complex W. Winkler, R. Herges Angew. Chem 2004, 116, 5955-5957 Angew. Chem. Int. Ed. Engl. 2004, 43, 5831-5833. cis-Bromination of Alkynes without Cationic Intermediates. R. Herges, A. Papafilippopoulos, K. Hess, C. Chiappe, D. Lenoir, H. Detert Angew. Chem. 2004, 117, 1437-1441. Angew. Chem. Int. Ed. Engl. 2004, 44, 1412-1416. MOL-VIC IP6.-GREBER ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) 1. C. Cepek, R. Fasel, M. Sancrotti, T. Greber and J. Osterwalder: Coexisting inequivalent orientations of C60 molecules adsorbed on Ag(100) Phys. Rev. B, 63, 125406 (2001). 2. J. Wider, F. Baumberger, M. Sambi, R. Gotter, A. Verdini, F. Bruno, D. Cvetko, A. Morgante, T. Greber and J. Osterwalder: Atomically resolved images from near node photoelectron holography experiments on Al(111) Phys. Rev. Lett. 86, 2337 (2001). 3. F. Baumberger, Th. Herrmann, A. Kara, S. Stolbov, N. Esser, T.S. Rahman, J.Osterwalder, W. Richter and T. Greber: Optical recognition of atomic steps on surfaces Phys. Rev. Lett. 90, 177402 (2003). 4. A. Tamai, W. Auwärter, C. Cepek, F. Baumberger, T. Greber and J. Osterwalder: One dimensional chains of C60 molecules on Cu(221) Surf. Sci. 566-568, 633 (2004). 5. F. Baumberger, M. Hengsberger, M. Muntwiler, M. Shi, J. Krempasky, L. Patthey, J. Osterwalder and T. Greber: Step lattice induced band gap opening at the Fermi level Phys. Rev. Lett. 92, 016803 (2004). 6. M. Muntwiler, W. Auwärter, A.P. Seitsonen, J. Osterwalder and T. Greber: Rocking motion induced charging of C60:C60 on h-BN/Ni(111) Phys. Rev. B, 71, 121402(R) (2005). 7. M. Corso, W. Auwärter, A. Tamai, T. Greber and J. Osterwalder: Boron Nitride Nanomesh Science, 303, 217 (2004). 8. R. Fasel, J. Wider, C. Quitmann, K.-H. Ernst and T. Greber: Determination of the absolute chirality of adsorbed molecules Angew. Chem. Int. Ed. 43, 2853 (2004). 9. F. Baumberger, M. Hengsberger, M. Muntwiler, M. Shi, J. Krempasky, L. Patthey, J. Osterwalder and T. Greber: Localization of surface states in disordered step lattices Phys. Rev. Lett. 92, 196805 (2004). 10. F. Baumberger, W. Auwärter, T. Greber and J. Osterwalder: Electron. coherence in a melting lead monolayer Science, 306, 2221 (2004). MOL-VIC AP1.-GOURDON ANNEX II: MOST RELEVANT PUBLICATIONS (last 5 years) 1.Grll, L. et al. Controlling the electronic interaction between a molecular wire and its atomic scale contacting pad. Nano Letters 5, 859-863 (2005). 2.Gross, L. et al. Scattering of surface state electrons at large organic molecules. Physical Review Letters 93 (2004). 3.Moresco, F. & Gourdon, A. Scanning tunneling microscopy experiments on single molecular landers. Proceedings Of The National Academy Of Sciences Of The United States Of America 102, 8809-8814 (2005). 4.Moresco, F. et al. Probing the different stages in contacting a single molecular wire. Physical Review Letters 91 (2003). 5.Moresco, F. et al. Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: A route to molecular switching. Physical Review Letters 86, 672-675 (2001). 6.Otero, R. et al. One-dimensional assembly and selective orientation of lander molecules on an O-Cu template. Angewandte Chemie-International Edition 43, 2092-2095 (2004). 7.Repp, J., Meyer, G., Stojkovic, S. M., Gourdon, A. & Joachim, C. Molecules on insulating films: Scanning-tunneling microscopy imaging of individual molecular orbitals. Physical Review Letters 94 (2005). 8.Rosei, F. et al. Organic molecules acting as templates on metal surfaces. Science 296, 328-331 (2002). 9.Rosei, F. et al. Properties of large organic molecules on metal surfaces. Progress In Surface Science 71, 95-146 (2003). 10.Sadhukhan, S. K., Viala, C. & Gourdon, A. Syntheses of hexabenzocoronene derivatives. Synthesis-Stuttgart, 15211525 (2003). 11.Viala, C., Seechi, A. & Gourdon, A. Synthesis of polyaromatic hydrocarbons with a central rotor. European Journal Of Organic Chemistry, 4185-4189 (2002). MOL-VIC IP1-ORTEGA.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) 1. “ Autoensamblado de nanoestructuras laterales y estudio de estados electrónicos” Funding agency: Spanish Ministry of Education Reference: MAT2002-03427 Total: 90.000 EURO 2. “One-dimensional molecular self-assembly on vicinal surfaces” Funding agencies: European Science Foundation, Spanish Ministry of Education Reference: MAT2002-12241-E Total: 81.650 EURO 3. “Caracterización experimental de la respuesta electrónica y óptica de nanoestructuras y sistemas de baja dimensionalidad”. Funding agency: Spanish Ministry of Education Reference: FIS2004-06490-C03-03 Total: 48.400 EURO MOL-VIC IP2-BERNDT.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) “Rastertunnelmikroskopie von Metallchalkogeniden und organischen Molekülen“ within FOR 353 „ChalkogenidSchichtstrukturen: Wachstum und Grenzfl¨achenph¨anomene“, 3 year postdoc position (BAT IIa), approx. 28 000 Euro consumables etc. MOL-VIC IP3-MICHEL.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) Requested (R) and obtained Title of the project Principal researcher (O) funding Funding agency and reference EURO Electron spectroscopies Enrique García Michel 120.000 (O) Dirección General de with high energetic Enseñanza Superior e (ARUPS) and spatial Investigación Científica (STM) resolution in low PB97-0031 dimensional systems Electronic localization Enrique García Michel 58.058 (O) Comunidad de Madrid and correlation effects 07N/0031/1998 in metal/semiconductor interfaces Development of UHV Enrique García Michel 124.950,41 (O) Dirección General de Technology and Enseñanza Superior e Instrumentation for Investigación Científica Synchrotron Radiation FPA2000-0026-P4-01 end-stations Growth of Enrique García Michel 33.176 (O) Comunidad de Madrid nanostructures by self07N/0056/2001 organization in stepped surfaces Electronic structure of Enrique García Michel 270.936,26 (O) Ministerio de Ciencia y quantum confined Tecnología systems BFM2001-0244 Electronic structure of Enrique García Michel 60.835 (O) Comunidad de Madrid self-assembled lateral 07N/0022/2002 nanostructures Electronic and Enrique García Michel 9.400 (O) Ministerio de Educación crystallographic y Ciencia structure of low FIS2001-00049 dimensional systems with high momentum resolution Electronic structure of Pilar Segovia Cabrero 40.825 (O) Comunidad de Madrid, self-organized molecular GR/MAT/0022/2004 systems at surfaces One-dimensional Enrique García Michel 51,300 (O) molecular self-assembly on vicinal surfaces (corresponds to the current MOL-VIC project) Collective phenomena Enrique García Michel 278,579(R) and quantum confinement in low dimensional systems Period 1/10/19981/10/2001 14/12/199814/12/2000 7/11/20016/11/2004 1/01/200231/12/2002 27/12/200126/12/2004 1/01/200331/12/2004 1/01/2005 31/12/2005 1/01/2005 31/12/2005 Ministerio de Ciencia y Tecnología 07/04/2004 MAT2002-11975-E 06/04/2007 Ministerio de Educación 2006-2008 y Ciencia FIS2005-00747 MOL-VIC IP4-HORN.- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) No applications. MOL-VIC IP5-HERGES- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) HE 1530/11-1 „Synthese Möbius-aromatischer Annulene; Moleküle mit nur einer -Seite“ (Synthesis of Moebius aromatic annulenes, molecules with a single side). The project is supported by the Deutsche Forschungsgemeinschaft. “Rational synthesis of carbon nanotubes”. We are aiming at the chemical synthesis of nanotubes with uniform geometries and thus well defined physical properties for the use in molecular electronics. “Design and synthesis of a light-driven proton pump”. Final goal is the uphill transport of protons through an artificial membrane or through a layer on a metal surface using photoswitchable molecules as carriers. Design and synthesis of “molecular plates and tripods” for the orthogonal orientation of photoswitchable molecules on Au surfaces. MOL-VIC IP6-GREBER- ANNEX III: APPLICATIONS ON RELATED SUBJECTS (last 5 years) Author SNF und PSI “Direct determination of adsorption induced structural changes in large molecules by Near Node Photoelectron Holography” (0.1 MEuro/2 years) ends 2006. Coauthor CERC3 “Time-resolved low energy electron diffraction from large molecules on surfaces” (0.03 MEuro/5 years) ends 2006. Coauthor of the SNF fundings of the group of J. Osterwalder 2005 (0.5 Meuro/2 years), ends 2007. Coauthor of STREP EU project “Boron Nitride Nanomesh as a Scaffold for Nanocatalysts and Functional Surfaces” (2 MEuro/3 years) ends 2008. SNF Swiss National Science Fundation PSI Paul Scherrer Institut MOL-VIC MOL-VIC Annex 4 Budget summary [Template] Please prepare this Annex by adding the separate budgets under A 9 (overall budget) and B7 of each IP (budget of each IP) together. MOL-VIC Overall budget of the CRP (A9 f): BUDGET ITEMS EUROCORES Funding Agency (EFA) Estimate of Funding PI 1 Ortega Ministerio de Educación y Ciencia (Spain) (in Euros) Salary costs Ph.D. student(s) Post-doc. Researcher(s) Senior researcher (s) Technician(s) Estimate of Funding PI 2 Berndt Deutsche Forshungsgemeinshaft (Germany) (in Euros) Estimate of Funding PI 3 Michel Ministerio de Educación y Ciencia (Spain) (in Euros) 3 x 56000 = 168000 2x35360=70720 Estimate of Funding PI 4 Horn Deutsche Forshungsgemeinshaft (Germany)) (in Euros) Estimate of Funding PI 5 Herges Deutsche Forshungsgemeinshaft (Germany)) (in Euros) 3 x 56000 = 168000 3 x 48000 = 144000 Estimate of Funding PI 6 Greber Swiss National Science Foundation (Switzerland) (in Euros) Estimate of TOTAL Funding (in Euros) 238753 789473 Guest Prof: 20000 32246 20000 32246 Equipment per item item 1 UV source + optics 19700 item 2 item 3 Item 4 Item 5 Travel conferences, worksh.,visits Consumables / Runn. Costs Including analysis costs Publication, Dissem. Cost Overheads if applicable Electron analyzer 133400 Quad. mass spectrom. 12000 UHV chamb. and gaug. 20000 Ion, turbo and rotary pumps, gate valves 20000 High Intens. Light sourc., fiber optic lamp 21000 Evaporator comp. 6000 HPLC software 8000 245100 Transfer rod: 5000 12000 12000 6000 14000 6300 50300 12000 15000 6000 32000 93000 2000 0 Channeltrons 5000 23 000 3000 19% 26927 0 20% 66860 19% 29906 5000 123693 Others Travel to synchrcotron 3000 187306 T O T A L 214700 171647 168000 0 administrative coordin. 2000 219000 403159 5000 1363812 MOL-VIC Requested budget for IP1 (IP1 – B1) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: MOL-VIC PI Name & Institution: Enrique Ortega, Universidad del País Vasco IP Nr:1 Funding Agency: Ministerio Educación y Ciencia (Spain) Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short Description of each budget item where appropriate Salary position Ph.D. student Post-doc. researcher senior researcher Technician student stipend / student assistant Equipment per item item 1 Electron analizer 133400 item 2 133400 item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs Conferences, workshops 4000 4000 4000 12000 Small parts, samples, evaporation material 4000 4000 4000 12000 26866 1520 1520 29906 including analysis costs Publication, Dissemination Costs Overheads 19% if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 168266 9520 ** If necessary, please also use the text box on the next page for additional description/justification of each budget item. 9520 187306 MOL-VIC Additional description/justification of budget items of IP1 (1 page maximum) High Resolution angular photoemission equipment: Self-assambled supramolecular structures exhibit an inherent degree of complexity, namely large, complex building-blocks (unit cells) and small interaction energies. In practice, systems are difficult to characterize with standard electron diffraction techniques, and hence the combination of powerful, sensitive techniques in both real (STM) and reciprocal space (photoemission) is necessary. The current proposal is intended to incorporate state-of-the-art high resolution, angular Photoemission (HR-ARPES) to the current set-up in San Sebastian, which includes Variable Temperature STM and standard electron diffraction techniques. The HR-ARPES equipment consists on a display-type electron analyzer that allowing simultaneous measurement of angle-resolved spectra within a 5º range, a plasma-discharge lamp and a monochromator. Only the full equipment ensures energy resolution below 10 meV and angular resolution down to 0.1º. The former is necessary for the small interacting energies (narrow bands and gaps), whereas the latter is critical to resolve band structures for extended states in large unit cells (for instance, to explore substrate mediated interactions): in fact, with the standard photon energy of 21 eV, the angular resolution becomes 0.005 Å-1, and hence assuming 10 points per Brillouin zone, the equivalent spatial resolution goes beyond 10 nm. MOL-VIC Requested budget for IP2 (IP2 – B1) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: MOL-VIC PI 2 Berndt, Kiel University: IP Nr: 2 Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding Short Description of each budget item where appropriate (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Complex experiments with interdisciplinary aspects 56000 56000 56000 UV-lamp setup for polymerisation experiments 19700 Salary position Ph.D. student Post-doc. researcher 168000 senior researcher Technician student stipend / student assistant Equipment per item item 1 19700 item 2 item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) 4000 4000 4000 12000 5000 5000 5000 15000 Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 84700 65000 ** If necessary, please also use the text box on the next page for additional description/justification of each budget item. 65000 214700 MOL-VIC Additional description/justification of budget items of IP2 (1 page maximum) Staff: The complexity of the planned experiments along with the interdisciplinary aspect of the work requires a post doctoral researcher. Equipment: To induce polymerisation an UV lamp (Lot-Oriel, 160-370 nm, 0.1 W/cm2) is required along with a power supply. The light will be focussed onto the sample in ultra-high vacuum using UV-grade lenses (Melles Griot), which can be approached to the sample by a translation stage (MDC). MOL-VIC Requested budget for IP1 (IP3 – B.2) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: Outline Proposal Nr(s).: 05SONS-OP-014 BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies Salary position Post-doc. Researcher IP Nr: 3 Duration where appropriate in month, including start date PI Name & Institution: Enrique Garcia Michel, Universidad Autonoma de Madrid Funding Agency solicited: Ministerio de Educación y Ciencia (Spain) YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] 24,1.1.2008 35360 Equipment per item Item 1 Item 2 35360 12000 20000 20000 5000 Item 3 Item 4 Travel conferences, workshops, travel to fieldwork, visits Short description/ justification of each budget item ** 70720 Salary of post-doc researcher 12000 20000 20000 5000 Quadrupole Mass Spectrometer UHV chamber and UHV gauge Turbo and rotary pumps, gate valve Transfer rod 2000 2000 2000 6000 Conferences, workshops, 2000 0 2000 1000 2000 1000 6000 2000 Small parts, samples, evaporation material Publication costs (including networking within the CRP) Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable 19% 9310 9948 7668 26927 1000 1000 1000 3000 Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 59310 63308 49028 Travel to synchrotron radiation facilities 171647 ** If necessary, please also use the text box on the next page for additional description/justification of each budget item. MOL-VIC Additional description/justification of budget items of IP3 (1 page maximum) The main budget item is related to scientific equipment needed to build a new sample preparation chamber adapted for the exposure to organic molecules, This includes pumps and accessories for sample cleaning (ion gun), and transfer (transfer rod). A QMS is also required to guarantee the quality and cleanliness of the molecular evaporations. Smaller budget items are required for consumables and travel to conferences and mutual visits. An important budget item is the application for the salary of a postdoctoral researcher during two years. The development of the activities described in the project, represent a significant increase of the work load, which cannot be undertaken without additional manpower. The postdoctoral researcher hired within this IP will take care of the operation of the SPALEED, data acquisition and analysis, with support from the rest of group. He/she will also be involved in the whole research activities related to this IP. MOL-VIC Requested budget for IP4 (IP4 –B2) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: MOL-VIC IP Nr: must be consistent with the rules set by the relevant national funding agencies Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] 56.000 56.000 Short Description of each budget item where appropriate Fritz-Haber-Institut DFG Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS K.Horn PI Name & Institution: 4 Salary position Ph.D. student Post-doc. researcher Scientific experiments on senior researcher supramolecular structures on Technician surfaces 56.000 168.000 student stipend / student assistant Equipment per item item 1 item 2 item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) TOTAL 56.000 56.000 ** If necessary, please also use the text box on the next page for additional description/justification of each budget item. 56.000 168.000 MOL-VIC Additional description/justification of budget items of IP4 (1 page maximum) This work needs a fully dedicated postdoctoral researcher to tackle the complexity of the experiments involved, and the command of the different experimental efforts and interpretation methods. MOL-VIC Requested budget for IP5 (IP5–B2) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: MOL-VIC IP Nr: must be consistent with the rules set by the relevant national funding agencies Rainer Herges, Unibersität Kiel Funding Agency: Outline Proposal Nr(s).: BUDGET ITEMS PI Name & Institution: Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short description/ justification of each budget item ** Salary position Ph.D. student Post-doc. Researcher 48.000 48.000 48.000 144.000 Design, synthesis and characterization of compounds High intensity light source SID-201, fiber optic coupler lamps , for photopolymerization and isomerization HPLC software and columns (accessories to existing instrument) senior researcher Technician student stipend / student assistant Equipment per item Item 1 21.000 21.000 Item 2 8.000 8.000 Item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) Consumables / Running Costs 4.000 5.000 5.000 14.000 10.000 12.000 10.000 32.000 including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 91.000 65.000 63.000 219.000 chemicals, glassware, analytics MOL-VIC Additional description/justification of budget items of IP5 (1 page maximum) The budget is mainly needed for the salary of a postdoc (36 months), chemicals, and equipment. For the photochemical polymerizations and the cis-trans isomerization of the surface bound retinal we need a tunable high-intensity light source e.g. the Model SID-201 from Photon Technology International. Standard equipment and the usual infrastructure (NMR, IR, UV, fluorescence MS etc.) for preparative chemistry is available in our institute. The travel budget should cover the expenses for mutual visits and for attending international meetings to present our results. MOL-VIC Requested budget for IP6 (IP6–B2) (The budget items have to be consistent with the rules of your national funding agency; Please contact them if you have questions about this matter): CRP Acronym: MOL-VIC IP Nr:6 Funding Agency solicited: Outline Proposal Nr(s).: BUDGET ITEMS must be consistent with the rules set by the relevant national funding agencies PI Name & Institution: GREBER, UZH Duration where appropriate in month, including start date YEAR 1 Funding YEAR 2 Funding YEAR 3 Funding TOTAL Funding (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] (in Euros) [other currencies] Short description/ justification of each budget item ** Salary position Ph.D. student Post-doc. Researcher 36/1 senior researcher 5/13 Technician 6/6 79’584 16’123 79’584 20’000 16’123 79’584 238’753 20’000 32’246 Guest Professor 6’000 Evaporator components Runs the Project at the Synchrotron Technician for special evaporator development student stipend / student assistant Equipment per item Item 1 6’000 Item 2 Item … Travel conferences, workshops, travel to fieldwork, visits (including networking within the CRP) 2’100 2’100 2’100 6’300 7’000 500 5’000 8’000 1’000 8’000 1’500 5’000 23’000 3’000 21’061 27’561 18’237 66’860 500 500 1’000 2’000 Consumables / Running Costs including analysis costs Publication, Dissemination Costs Overheads if applicable Others including access to large infrastructures, shiptime, etc. (please specify) T O T A L 126’866 165’868 110’423 403’159 Channeltrons MOL-VIC Additional description/justification of budget items of IP6 (1 page maximum) The budget mainly consists in salaries, running costs for the experiment, travel and publication money. We ask for salaries of a postdoc (36 month) and a technician (6 month) and for the expenses of a guest professor (5 month). The postdoc position is necessary in order to run the above mentioned XPD experiment at the Swiss Light Source, and to train students on the PhD and the graduate level. The technician position is necessary in order to further develop the difficult task to evaporate large molecules of which nanogram quantities were available, only. The money for a guest is important in order to fertilize the research, in particular in view of the theoretical understanding of the results. We furthermore expect from this guest to help to maximize synergies inside and outside MOL-VIC and to develop new opportunities and views in the field of self organized nano-structures. The surface physics group at UZH will contribute the salary of the PI, who will work about 30% on MOL-VIC, and potential PhD students on the project. A contribution to the running costs for the experiments is expected. E.g. the consumable “channeltrons” has to be covered from inside MOL-VIC. The surface physics group of Prof. Dr. Jürg Osterwalder and the physics institute at UZH will add about an equal amount to the running costs and the infrastructure of IP6. Travel and publication money is important for the networking inside MOL-VIC and the dissemination of the results to the world-wide community. Again, the outside contribution from the surface physics group and the physics institute at UZH will be about an equal amount to travel and publication money of IP6.