La misión de la UNIVERSIDAD es el desarrollo
social, económico y cultural de la sociedad de
su entorno a traves de la creación y transmisión
de CONOCIMIENTOS, ofreciendo una docencia
de calidad y desarrollando una investigación
avanzada de acuerdo con exigentes criterios
internacionales.
José Ortega y Gasset acuñó una
metáfora
sumamente
útil
para
comprender intuitivamente la situación de
nuestro tiempo:
La cultura es el esfuerzo permanente que
un nadador realiza para mantenerse a
flote.
Manuel Azaña:
Si cada español hablara de lo que sabe y
solo de lo que sabe, se haría un gran
silencio
nacional
que
podríamos
aprovechar para estudiar
The large investments in research and education made in
recent years have provided Brazilian scientists with the
conditions to achieve scientific excellence.
NATURE MATERIALS | VOL 9 | JULY 2010 |527
WWW.NATURE.COM/NATUREMATERIALS
W.J. Parak, ACS Nano, 4, 4333 (2010)
Nanoscience research crosses disciplines and has incorporated knowledge from many fields
Theoretical and Computational
Nanotechnology:
Fundaments and Applications.
Prof. Juan Andrés
Juan Andres Bort
Work address:
Department of Physical and Analytical Chemistry, Universitat Jaume I,Castelló(Spain)
Graduation: Chemistry, 1978, Universitat de Valencia
Ph.D. dissertation: Chemistry,1982, Universitat de Valencia
Current position: 1994, Full Professor, Physical Chemistry, Universitat Jaume I
ACADEMIC MANAGEMENT
- Director of International relationships (2 years)
- Director of the Department of Experimental Sciences (7 years)
- Vice-rector of Scientific and Technological Promotion, Universitat Jaume I (5 years)
PUBLICATIONS
- Articles: 305 published + 7 submitted for publication.
- Books: 15 published (text books)
- Book Chapters: 10 published (research)
- 2 published Book as Co-editor
MAIN LINES OF RESEARCH
Electronic structure and chemical reactivity.
Molecular mechanics of chemical reactions.
Enzyme Catalysis: Quantum Mechanics (QM)/Molecular Mechanics(MM)
and Molecular Dynamics studies.
Theoretical organic, organometallic and biological chemistry.
Topological analysis of electronic distribution.
Electric and magnetic properties of materials.
High pressure effects in materials.
Growth, crystallization and formation processes in crystals.
Optical properties of materials.
Diffusion processes in solid state
h index= 37, more than 4600 citations.
-Theses supervised: 18 Ph. D.
- More than 40 research projects as principal research, funded by European
Community, Ministerio de Educación y Ciencia, Generalitat Valenciana,
Fundación Bancaixa-UJI
-More than 400 communications at both national and international
congresses.
-More than 20 as Invited Speaker in international congresses and 5 in national
congresses.
- 5 as Chairman in international congresses and 2 in national congresses.
-15 Conferences in different Universities of Brazil, Chile, France, Italy and
Sweden.
-14 Conferences in different Universities of Spain (Barcelona, Cádiz, Gerona,
Granada, La Coruña, Madrid, Oviedo, País Vasco, Santiago de Compostela,
Sevilla, Valencia, Zaragoza) .
Acknowledgments
Dr. Mario Moreira
Dr. Diogo Volanti
Dr. Valeria Longo
Dr. Marcelo Orlandi
Prof. Jose A. Varela
Prof. Elson Longo
Prof. Edson Leite
(CMDCM, Sao Carlos and Araraquara, Brazil)
Prof. Armando Beltrán
Dr. Lourdes Gracia
(Universitat Jaume I)
Dr. Julio Sambrano (Bauru)
Dr. Fabricio Sensato (Sao Paulo)
Daniel Stroppa (Campinas)
Brazilian agencies Fapesp and CNPq by the financial support,.
Research funds provided by the Ministerio de Educación y Cultura of the
Spanish Government.
Docent Stay supported by Universitat Jaume I-Banco Santander
Chapter 1. Introduction, perspectives, and aims. On the science
.
of simulation and modelling. Modelling at bulk, meso, and nano
scale. (2 hours).
Chapter 2. Experimental Techniques in Nanotechnology. Theory
and Experiment: “Two faces of the same coin” (2 hours).
Chapter 3. Introduction to Methods of the Classic and Quantum
Mechanics.
Force
Fields,
Semiempirical,
Plane-Wave
pseudpotential calculations. (2 hours)
Chapter 4. Intoduction to Methods and Techniques of Quantum
Chemistry, Ab initio methods, and Methods based on Density
Functional Theory (DFT). (4 hours)
Chapter 5. Visualization codes, algorithms and programs.
GAUSSIAN, CRYSTAL, and VASP. (6 hours).
.
Chapter 6. Calculation of physical and chemical properties of
nanomaterials. (2 hours).
Chapter 7. Calculation of optical properties. Photoluminescence.
(3 hours).
Chapter
8.
Modelization
of
the
growth
mechanism
of
nanomaterials. Surface Energy and Wullf architecture (3 hours)
Chapter
9. Heterostructures Modeling. Simple and complex
metal oxides. (2 hours)
Chapter 10. Modelization of chemical reaction at surfaces.
Heterogeneous catalysis. Towards an undertanding of the
Nanocatalysis. (4 hours)
Chapter 1. Introduction, perspectives,
and aims. On the science of simulation
and modelling. Modelling at bulk,
meso, and nano scale.
Juan Andrés
Departamento de Química-Física y Analítica
Universitat Jaume I
Spain
&
CMDCM, Sao Carlos
Brazil
Sao Carlos, Octubro 2011
How
computational/theoretical
chemists can be useful in the
field of
nanoscience/nanotechnology?
What can a
theoretical/computational chemist
bring to the experimentalist active
in the devolopment of
nanoscience/nanotechnology ?
“It is the goal of this Course to present in one place the key
features, methods, tools, and techniques of Theoretical and
Computational Nanotechnology, to provide examples where
Theoretical and Computational Chemistry has produced a major
contribution to multidisciplinary efforts, and to point out the
possibilities and opportunities for the future.”
“Maybe it is because I work on quantum mechanics, but I think
that the big challenge in materials science in general as well as in
Naoscience and Nanotechnology in particular is understanding
how quantum mechanics influences materials at the microscopic
level.”
Simulation techniques are playing an increasingly important role in
the burgeoning field of nanotechnology. Arguably the
nanotechnology revolution, which has seen a worldwide
investment of more than $42 billion dollars over the last decade,
was seeded both by developments in analytical techniques
capable of characterising down to the nanoscale and by
developments in computational hardware and techniques capable
of modelling structures at that length scale.
Atomistic simulation (molecular mechanics and dynamics,
quantum mechanics and field based approaches) has played an
important role in nanoscience: predicting nanostructure and
revealing mechanisms for intriguing nanoscale behaviors.
Experimental nanoscience has provided a valuable source of data
for the validation of simulation techniques, basis sets and forcefields.
As
nanoscience
is
increasingly
turned
into
nanotechnologies, computer simulation methods can play a
critical role.
Experimental nanoscience has provided a valuable source of data
for the validation of simulation techniques, basis sets and forcefields.
As
nanoscience
is
increasingly
turned
into
nanotechnologies, computer simulation methods can play a
critical role.
General Considerations 1
An overview of some of the theoretical
questions that remain to be answered, is a
useful first step towards designing new
fundamental research programs (combining
both
experimental
and
theoretical
investigations).
General Considerations 2
I hope that this original approach will be
useful to experimentalists wishing to carry
out fundamental studies of nanostructures,
and to theoreticians who are looking for
new challenges.
General Considerations 3
It should be emphasized that this
problem area is not just of academic
interest. All the questions mentioned
above have direct relevance for
different
physical
and
chemical
phenomena.
General Considerations 4
This course provides an exemplary
overview of research on this topic,
from simple model systems where
first qualitative explanations start to
be successful, up to more realistic
complex systems which are still
beyond our understanding.
Outline
Introduction
– Nanoscience, Nanotechnology
– History
– Methods of Theoretical & Computational
Chemistry
– Challenges
Nature has evolved highly complex and
elegant mechanisms for materials and
synthesis. Living organisms produce
materials with physical properties that
still surpass those of analogous synthetic
materials
with
similar
phase
compositions.
Nature has long been using the bottomup nanofabrication method to form selfassembled nanomaterials that are much
stronger and tougher than many manmade materials formed top-down.
The term “nano” is derived from the Greek word for “dwarf”,
“nanos”. This etymology, and its placement on the metric scale
(1 nm=10-9 m), make it clear that tiny dimensions not visible to
the naked eye, beyond the normal limits of our observation,
are involved. Approaching it from familiar terrain may make the
“nanoworld” more easily accessible (Figure 1).
Characteristic of nanoparticles, besides their small size, is their vast surface
area. A simple thought experiment will serve to illustrate this concept (Figure
2). Take a cube with edges 1 cm in length—roughly the size of a sugar
cube—at divide it step by step into cubes with edges 1 nm in length.
While the sum of the volumes remains the same, the number
of individual cubes and their total surface area increases
dramatically.
The surface area of the 1021 “nanocubes”, at 6000 m2, amounts to roughly
the area of a football field (ca. 7000 m2)—created from a single sugar cube!
Compared to an infinite three-dimensional solid (aptly expressed by the term
“bulk”), with nanoparticles we may expect that their physicochemical
properties are strongly influenced, if not indeed dominated, by the surface.
Unsaturated bonding sites and unoccupied coordination sites will play a
major role, compared to a highly ordered crystalline solid
A nanomaterial is commonly defined as an object with dimensions of 1–100
nm, which includes nanogels, nanofibers, nanotubes and nanoparticles (i.e.
spheres, rods and cubes).
NMs can have various applications in areas such as electronics, clothing,
food packaging, paint, surface modifications, additives in food packaging and
drugs. It is expected that the sale of products employing nanotechnology
may reach $1 trillion per year by 2015, with medical-related products alone
occupying $53 billion in this market.
In August 2009, there were more than 1000 nanotechnology incorporated
products marketed by 485 companies in 24 countries.
W. W. I. C. f. Scholars, Consumer Products: An Inventory of
Nanotechnology-based Consumer Products Currently on theMarket, 2010,
http://www.nanotechproject.org/inventories/consumer/,
T. Xia, N. Li and A. E. Nel, Annu. Rev. Public Health, 2009, 30,137. C. F.
Jones and D. W. Grainger, Adv. Drug Delivery Rev., 2009, 61, 438.
Nanomaterials are of immense importance in today’s modern society. The
development of chemical industries, environmental protection and newenergy resources (e.g., fuel cells, lithium ion batteries) have long relied on
nanomaterials with exceptional properties.
The fields of catalysis, electrocatalysis, photocatalysis and photoelectricity
are all examples of where nanotechnology is impacting on current
science.1–4
1 C. Burda, X. B. Chen, R. Narayanan and M. A. El-Sayed, Chem. Rev.,
2005, 105, 1025.
2 M. Haruta, CATTECH, 2002, 6, 102.
3 D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem., Int. Ed., 2005, 44,
7852.
4 M. C. Daniel and D. Astruc, Chem. Rev., 2004, 104, 293.
As particle dimensions reduce towards the nanoscale, the surface-to-volume
ratio proportionally increases and smallsize effects associated with
nanoparticles become more pronounced.
Understanding the nanoscale topography of surface sites, such as terraces,
steps, kinks, adatoms and vacancies, and their effects on catalytic and other
physicochemical properties is the key to designing nanoscale functional
materials by nanotechnology.5–7
5 G. A. Somorjai, Science, 1978, 201, 489.
6 F. Tao and M. Salmeron, Science, 2011, 331, 171.
7 D. L. Feldheim, Science, 2007, 316, 699.
The performance of nanocrystals used as catalysts depends strongly on the
surface structure of facets enclosing the crystals. Thermodynamics usually
ensures that crystal facets evolve to have the lowest surface energy during
the crystal growth process. For a pure metal, the surface energy relies on
coordination numbers (CNs) of surface atoms as well as their density. For
example, it increases in the order of g{111} < g{100} < g{110} < g{hkl} on a
face-centered cubic (fcc) metal, where {hkl} represents high-index planes
with at least one Miller index larger than 1.8,9
8 Z. L. Wang, J. Phys. Chem. B, 2000, 104, 1153.
9 Y. N. Wen and H. M. Zhang, Solid State Commun., 2007, 144,
163.
For a metal oxide, the surface energy increases with increasing density of
dangling bonds. Generally, high-energy surfaces have an open surface
structure and possess exceptional properties.
Long-term fundamental studies in surface science have shown that Pt highindex planes with open surface structure exhibit much higher reactivity than
that of (111) or (100) low-index planes, because high-index planes have a
large density of low-coordinated atoms situated on steps and kinks, with high
reactivity required for high catalytic activity.10–12
10 N. P. Lebedeva, M. T. M. Koper, J. M. Feliu and R. A. van Santen, J.
Phys. Chem. B, 2002, 106, 12938.
11 S. L. Bernasek and G. A. Somorjai, Surf. Sci., 1975, 48, 204.
12 S. G. Sun, A. C. Chen, T. S. Huang, J. B. Li and Z. W. Tian, J. Electroanal.
Chem., 1992, 340, 213.
More importantly, on high-index planes, there exist short-range steric sites
(such as ‘‘chair’’ sites) that are considered as active sites and consist of the
combination of several (typical 5–6) step and terrace atoms.13,14
13 R. A. Van Santen, Acc. Chem. Res., 2009, 42, 57.
14 N. Tian, Z. Y. Zhou and S. G. Sun, J. Phys. Chem. C, 2008, 112, 19801.
Due to synergistic effect between step and terrace atoms, steric sites usually
serve as catalytically active sites. Besides, open-structure surfaces also play
a very important role in the charging/discharging process of lithium ion
batteries. They can provide parallel channels, where Li+ ions are able to
intercalate through the surface with the least resistance compared to other
crystal plane orientations.15 This favors fast ion transfer between surface
and interior.
15 G. Z. Wei, X. Lu, F. S. Ke, L. Huang, J. T. Li, Z. X. Wang, Z. Y. Zhou and
S. G. Sun, Adv. Mater., 2010, 22, 4364.
Normally, nanocrystals with low surface energy such as those formed under
normal conditions usually have low catalytic activities. Those with high
surface energies are known to possess enhanced catalytic properties.
The goal here is to create nanocrystal catalysts which have high surface
energy facets. Unfortunately, this presents a big challenging. When a crystal
grows, different facets grow with different rates. High-energy facets typically
have higher growth rates than low-energy facets. Overall, the final crystal
shape is dominated by the slow-growth facets that have low surface
energy.16
16 H. E. Buckley, Crystal Growth, Wiley, New York, 1951.
Remarkably, substantial progress has been made in overcoming the
obstacle to form nanocrystals with high-energy facets in recent years.30–32
30 N. Tian, Z. Y. Zhou, S. G. Sun, Y. Ding and Z. L. Wang, Science, 2007,
316, 732.
31 H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M.
Cheng and G. Q. Lu, Nature, 2008, 453, 638.
32 Z. Y. Jiang, Q. Kuang, Z. X. Xie and L. S. Zheng, Adv. Funct. Mater.,
2010, 20, 3634.
Although there are several excellent reviews about shape controlled
synthesis of metal nanocrystals, they mainly describe nanocrystals with lowenergy facets.28,33,34
28 Z. M. Peng and H. Yang, Nano Today, 2009, 4, 143.
33 A. R. Tao, S. Habas and P. D. Yang, Small, 2008, 4, 310.
34 Y. Xia, Y. J. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem.,
Int. Ed., 2009, 48, 60.
In this review, after a brief introduction of the relationship between surface
structure and crystal shapes, we focus on the recent progress made in
shape-controlled synthesis of metal nanocrystals with high-energy facets and
open surface structure, including high-index facets and {110} facets,
especially electrochemically shape-controlled synthesis of Pt-group metal
nanocrystals.
Z.-Y. Zhou, N. Tian, J.-T. Li, I. Broadwell and S.-G. Sun, Nanomaterials of
high surface energy with exceptional properties in catalysis and energy
storage, Chem. Soc. Rev., DOI: 10.1039/c0cs00176g
Engineering the shapes of semiconducting functional materials to desirable
morphologies has long been actively pursued. This is because many
applications such as heterogeneous catalysis, gas sensing and ion
detecting, molecule adsorption, energy conversion and storage are very
sensitive to surface atomic structures, which can be finely tailored by
morphology control.
From the intensive studies on morphology-controlled materials in the past
decades, significant advancements in this area have been achieved.1–29
1 S. E. Habas, H. Lee, V. Radmilovic, G. A. Somorjai and P. Yang, Nat.
Mater., 2007, 6, 692.
2 C. K. Tsung, J. N. Kuhn, W. Y. Huang, C. Aliaga, L. I. Hung, G. A. Somorjai
and P. D. Yang, J. Am. Chem. Soc., 2009, 131, 5816.
3 A. Tao, P. Sinsermsuksakul and P. D. Yang, Angew. Chem., Int. Ed., 2006,
45, 4597.
4 A. I. Hochbaum and P. D. Yang, Chem. Rev., 2010, 110, 527.
5 Y. Xia, Y. J. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem., Int. Ed.,
2008, 48, 60.
6 B. Wiley, Y. G. Sun, J. Y. Chen, H. Cang, Z. Y. Li, X. D. Li and Y. N. Xia,
MRS Bull., 2011, 30, 356.
7 B. Lim, H. Kobayashi, T. Yu, J. G. Wang, M. J. Kim, Z. Y. Li, M. Rycenga
and Y. Xia, J. Am. Chem. Soc., 2010, 132, 2506.
8 Y. J. Xiong and Y. N. Xia, Adv. Mater., 2007, 19, 3385.
9 B. Wiley, Y. G. Sun, B. Mayers and Y. N. Xia, Chem.–Eur. J., 2005, 11, 454.
10 B. Sadtler, D. O. Demchenko, H. Zheng, S. M. Hughes, M. G. Merkle, U.
Dahmen, L. W. Wang and A. P. Alivisatos, J. Am. Chem. Soc., 2009, 131,
5285.
11 Y. D. Yin, C. Erdonmez, S. Aloni and A. P. Alivisatos, J. Am. Chem. Soc.,
2006, 128, 12671.
12 X. J. Feng, J. Zhai and L. Jiang, Angew. Chem., Int. Ed., 2005, 44, 5115.
13 X. L. Li, Q. Peng, J. X. Yi, X. Wang and Y. D. Li, Chem.–Eur. J.,
2006, 12, 2383.
14 X. Wang, J. Zhuang, Q. Peng and Y. D. Li, Nature, 2005, 437, 121.
15 Y. G. Sun and Y. N. Xia, Science, 2002, 298, 2176.
16 F. Wang, Y. Han, C. S. Lim, Y. H. Lu, J. Wang, J. Xu, H. Y. Chen, C.
Zhang, M. H. Hong and X. G. Liu, Nature, 2010, 463, 1061.
17 B. Lim, M. J. Jiang, P. H. C. Camargo, E. C. Cho, J. Tao, X. M. Lu, Y. M.
Zhu and Y. A. Xia, Science, 2009, 324, 1302.
18 N. Tian, Z. Y. Zhou, S. G. Sun, Y. Ding and Z. L. Wang, Science, 2007,
316, 732.
19 X. W. Xie, Y. Li, Z. Q. Liu, M. Haruta and W. J. Shen, Nature, 2009, 458,
746.
20 X. D. Feng, D. C. Sayle, Z. L. Wang, M. S. Paras, B. Santora, A. C.
Sutorik, T. X. T. Sayle, Y. Yang, Y. Ding, X. D. Wang and Y. S. Her, Science,
2006, 312, 1504.
21 H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M.
Cheng and G. Q. Lu, Nature, 2008, 453, 638.
22 X. G. Peng, L. Manna, W. D. Yang, J. Wickham, E. Scher, A. Kadavanich
and A. P. Alivisatos, Nature, 2000, 404, 59.
23 J. H. Xiang, S. H. Yu, B. H. Liu, Y. Xu, X. Gen and L. Ren, Inorg. Chem.
Commun., 2004, 7, 572.
24 C. Z. Wu and Y. Xie, Chem. Commun., 2009, 5943.
25 X. G. Han, M. S. Jin, S. F. Xie, Q. Kuang, Z. Y. Jiang, Y. Q. Jiang, Z. X.
Xie and L. S. Zheng, Angew. Chem., Int. Ed., 2009, 48, 9180.
26 C. Burda, X. B. Chen, R. Narayanan and M. A. El-Sayed, Chem. Rev.,
2005, 105, 1025.
27 X. Chen and S. S. Mao, Chem. Rev., 2007, 107, 2891.
28 H. C. Zeng, J. Mater. Chem., 2006, 16, 649.
29 H. G. Yang and H. C. Zeng, Angew. Chem., Int. Ed., 2004, 43, 5930.
Crystal facet engineering of semiconductor photocatalysts: motivations,
advances and unique properties
G. Liu, J. C. Yu, G. Q. Luc and H.-M. Cheng.
Chem. Comm, DOI: 10.1039/c1cc10665a
Dominance of broken bonds and nonbonding electrons at the
nanoscale,
Chang Q Sun, Nanoscale, 2010
Materials at the nanoscale demonstrate novel properties of two types.
One is the size and shape induced tunability of the otherwise constant
quantities associated with bulky species. For example, the elastic
modulus, dielectric constant, conductivity, melting point, etc, of a
substance no longer remain constant but change with its shape and
size; the other is the emergence of completely new properties that
cannot be seen from the bulk such as the extraordinary high capability
for catalysis, nonmagnetic–magnetic and conductor–insulator
transitions. These two entities form the foundations of nanoscience and
Nanotechnology that has been recognized as one of the key drivers of
science, technology and economics in the 21st century.
Nanoscience 1
Originating from the fields of physics,
chemistry, materials science, and chemical
engineering, this area of study is now often
referred to as nanoscience.
Nanoscience 2
Nanostructured materials such as
nanoparticles, nanotubes, nanowires
(nanorods), nanoribbons (nanobelts),
nanotapes,
nanorings,
nanoplates,
nanotriangles, nanosheets, nanoballs
and nanohelices,
Nanoscience 3
ALL IS NANO !
…..have attracted extensive attention
due to their properties with important
and
potential
applications
in
constructing nanoscaled electronic and
opto-electronic devices, gas sensors,
catalysts, and thin growth.
Feymann, R. P. Eng. Sci. 23, 22 (1960).
“The
principle of Physics as far as I can
see, do not speak against the possibility
of maneuvering things atom by atom.”
Where are we?
TODAY THE QUEST FOR NOVEL MATERIALS WITH DISTINCT PROPERTIES
FOR CRITICAL TECHNOLOGICAL APPLICATIONS HAS MOTIVATED A
CONSITENT EFFORT IN BETTER UNDERSTANDING SOLID-STATE
PROCESSES, BOTH EXPERIMENTALLY AND FROM THEORY
THE PROGRESS OF THE PAST DECADES ON NANOMATERIALS HAVE
SHOWN THAT BULK PROPERTIES BREAK DOWN ON CROSSING LOWER SIZE
LIMITS, UNFOLDING A RICH SET OF NEW PHYSICAL AND CHEMICAL
PROPERTIES AND OPENING NEW SYNTHETIC ROUTES
FOR THE SYNTHETIC EFFORTS TO FULLY TAKE ADVANTAGE OF SUCH
PECULIAR PROPERTIES, A PRECISE AND FIRM ATOMISTIC UNDERSTANDING
IS MANDATORY
SIMULATIONS OF REAL MATERIALS UNDER CONDITION CORRESPONDING
TO THE EXPERIMENTS ARE SHEDDING LIGHT ONTO YET ELUSIVE ASPECTS
ACCORDINGLY, A NEW WAY OF BRIGING TOGETHER THEORY,
IMPLEMENTATION OF SIMULATION STRATEGIES AS A POWEFUL SUPPORT
TO THE EXPERIMENTS IS EMERGING.
Where are we?
THE DEVELOPMENT AND IMPLEMENTATION OF FIRSTPRINCIPLE METHODS AND TECHNIQUES ALLOW TO CARRY
OUT CALCULATIONS TO QUANTITATIVELY PREDICT AND
EXPLAIN THE PHYSICAL AND CHEMICAL PROPERTIES OF
MATERIALS.
ELECTRONIC STRUCTURE THEORY PROVIDES BOTH
CONCEPTUAL UNDERSTANDING AND COMPUTATIONAL
TOOLS TO CALCULATE IT.
ADVANCE IN THEORETICAL METHODS AND TECHNIQUES AS
WELL AS COMPUTATIONAL POWER HAVE HAD A
TREMENDOUS IMPACT IN MATERIALS SCIENCE
OF COURSE, THEORETICAL GUIDANCE NEEDS TO BE USED
IN A COOPERATIVILY MANNER WITH THE ACCUMULATED
EXPERIENCE OF EXPERIMENTAL EXPLORERS.
Where are we?
DURING THE LAST YEARS ELECTRONIC
STRUCTURE THEORY DEVELOPED FROM A
DESCRIPTIVE TO AN ANALYTICAL TOOL AND IS
NOW AN INTEGRAL PART OF RESEARCH WITH
IMPORTANT CONSEQUENCES:
1. FACILITING THE INTERPRETATION AND
RATIONALIZATION OF EXPERIMENTAL RESULTS
2. HELPING TO UNCOVER ESSENTIAL CRYSTAL
STRUCTURE-PROPERTY RELATIONSHIPS
3. DIRECTING FURTHER
Computer simulation methods in physical chemistry: Large
molecules, fluids and solids
Annual Meeting of the Deutsche Bunsen-Gesellschaft für Physikalische Chemie,
Stuttgart, May 24-26, 2001
“Science is undergoing a structural transition from two broad methodologies
to three, namely from experimental and theoretical science to include the
additional category of computational and information science. A comparable
example of such a change occurred with the development of systematic
experience science at the time of Galileo” — Advanced Scientific
Computing Committee of the US National Science Foundation.
J. Brickmann and J. Sauer, Phys. Chem. Chem. Phys., 2001, 3
In silico methods are a valid tool for
analysing the properties of materials
and interest in computational modelling
techniques
to
predict
their
physical/chemical
properties
is
constantly growing.
Experiment
Real
Word
Classification
Abstraction
Simplification
Approximation
Generalization
Experimental
Data
Theory
Applying
Theoretical Methods,
Computing Techniques
and Mathematical
Algorithms
Comparing is testing
Model of
the Word
Simulation
Predictions
Three Important Turns in
Science
Thales 600 BC
ObserveModel
Galileo 1500 BC Model  Design Experiment  ObserveModel
Rahman
and Parrinello
Mimic Reality on a Computer  ObserveModel
“Crystal Structure and Pair Potentials. A Molecular Dynamics Study”
Physical Review Letters, 45, 1196 (1980)
Modified from:
van Gunsteren et al., Angew. Chem. Int. Ed. Engl, 45, 4064 (2006)
“Computations on complex systems are, in my opinion,
the current frontier of theoretical chemistry”
D. G. Truhlar
Molecular Modeling of Complex Chemical Systems
J. Am. Chem. Soc., 2008, 130, 16824-16827
56
“THE ETERNAL MISTERY OF THE
WORLD IS ITS COMPREHENSIBILITY.
THE FACT THAT IT IS
COMPREHENSIBLE IS A MIRACLE”
ALBERT EINSTEIN
CLUSTER-ASSEMBLED MATERIALS
Fullerenes, atomic clusters, and larger inorganic nanocrystals can be used as
assembly elements for creating materials with tailored properties.
S. A. Claridge, A. W. Castleman, S. N. Khanna, C. B. Murray, A. Sen, P. S. Weiss, ACS
Nano 2009, 3, 244.
58
SHAPE-CONTROLLED
SYNTHESIS OF METAL
NANOCRYSTALS
Reaction pathways that lead
to fcc metal nanocrystals
having different shapes. First,
a precursor is reduced or
decomposed to form the
nuclei (small clusters). Once
the nuclei have grown past a
certain size, they become
seeds with a single-crystal,
singly twinned, or multiply
twinned structure. If stacking
faults are introduced, then
plate-like seeds will be
formed.
59
Y. Xia, Y. Xiong, B. Lim, Sara E. Skrabalak, Angew. Chem. Int. Ed. 2009, 48, 60.
Microscopic and macroscopic behaviors of nanoparticles depend on
a number of a number of important characteristics and properties
V. H. Grassian
J. Phys. Chem. C 2008, 112, 18303
A. Greenberg
VOL. 3 ▪ NO. 4 ▪ 762 ▪ 2009
The world today is facing increasing energy demands and
simultaneously demand for cleaner and more environmentally
friendly technologies.
The development of new nanomaterials is expected to have a
major impact on the development of novel sustainable energy
technologies.
- Bérube, V.; Radtke, G.; Desselhaus, M.; Chen, G. Size Effects on the Hydrogen
Storage Properties of Nanostructured Metal Hydrides: A Review. Int. J. Energy Res.
2007, 31, 637.
- Bérube, V.; Chen, G.; Dresselhaus, M. S. Impact of Nanostructuring on the
Enthalpy of Formation of Metal Hydrides. Int. J. Hydrogen Energy 2008, 33, 4122.
Schlapbach, L.; Zu¨ ttel, A. Hydrogen-Storage Materials forMobile Applications.
Nature 2001, 414, 353.
- Eberle, U.; Felderhoff, M.; Schüth, F. Chemical and Physical Solutions for
Hydrogen Storage. Angew. Chem., Int. Ed. 2009, 48, 6608.
- Orimo, S.; Nakamori, Y.; Eliseo, J. R.; Zuüttel, A.; Jensen, C. M. Complex Hydrides
for Hydrogen Storage. Chem. Rev. 2007,107, 4111.
- Dornheim, M.; Eigen, N.; Barkhordarian, G.; Klassen, T.; Bormann, R. Tailoring
Hydrogen Storage Materials towards Application. Adv. Eng. Mater. 2006, 8, 377.
Nanotechnology is currently undergoing an
impressive expansion in material science research and
development of systems that have novel properties due to
their small size.
Most of the research efforts have been focused on
applications, while the implications efforts (i.e.,
environmental health and safety) have lagged behind.
As a consequence, the success of nanotechnology
will require assurances that the products being developed
are safe from an environmental, health, and safety
standpoint.
D. B. Warheit, Nano Letters, 2010
These concerns have led to a debate among
governmental agencies and advocacy groups on
whether implementation of special regulations
should be required for commercialization of
products containing nanomaterials.
Therefore the assessments of nanomaterialrelated health risks must be accurate and verifiable.
D, B. Warheit, Nano Letters, 2010
The relative dearth of substantive hazard data on
nanomaterials, concomitant with an abundance of
high-dose, in vitro cellular findings has created a
perception that the vast majority of nanoparticles
are highly toxic.
Evaluations of human health and ecological
implications of nanoparticle exposures will be
required to attain full commercialization potential.
D. B. Warheit, Nano Letters, 2010
Schematic showing the evolution of modern surface science
Gabor A. Somorjai and Jeong Y. Park
Examples
In2O3 Nanoparticles
Z.R. Dai et al., J. Phys. Chem. B 106 (2002) 902.
Nanoribbons – Nanobelts – Nanosheets
GaO
A. Murali et al. Nano Letters 1 (2001) 287.
Examples
C60 Fullerene
http://www.photon.t.u-tokyo.ac.jp/~maruyama/fticr/ft-icr.html
Examples
Au55 Nanowires on SiO2
N. Lu et al., Nano Letters, 2 (2002) 1097.
Nanotapes Co0.05Ti0.95O2@SnO2
R. He et al. Nano Letters 2 (2002) 109.
Examples
Nanohelices
Lefthanded Ag helices
Carbon Nanotubes
A. Koshio et al., Nano Letters 2 (2002) 995.
C. Zhan et al., Langmiur, 19 (2003) 9440.
Examples
Nanotriangles
N. Pinna et al. Langmuir, 17 (2001) 7982.
Nanosheets
S.-H. Yu et al. Adv. Mater. 7 (1995) 607.
Examples
Fe Nanorods
S-J. Park, J. Am. Chem.Soc. 122 (2000) 8581
Ni Nanorings
K.L. Hobbs et al., Nano Letters, 4 (2004) 167
and……
Examples
…MoS2 nanoflowers
Y. B. Li et al, Appl. Phys. Lett. 82 (2003) 1962.
Nanoscience, Nanotechnology, and Chemistry
G. M. Whitesides, Small 2005, 1, 172
Nanoscience is now a thread woven into many fields of science.
Nanotechnology—certainly evolutionary, and perhaps
evolutionary—will emerge from it. Chemistry will play a role;
whether this role is supporting or leading will depend in part on
how the field develops and what opportunities emerge, and in
part on how imaginative and aggressive chemists and chemical
engineers are, or become, in finding their place in it.
Since there are few new, high-margin markets open to the chemical
industry, it may need to move downstream— uncomfortable though it
may be to do so—in nanotechnology (or other emerging areas) if it is
not to stagnate technically and financially. Competition in new markets
requires agility, and the ability to move quickly to capture new
opportunities is always a difficult trick. It will be particularly difficult for
an industry that, for some decades, has not been rewarded for
embracing new ideas or for accomplishing new tricks, and that, through
lack of practice, has become unaccustomed to doing so.
Nanotechnology 1
From here the nanotechnology is achieved
Nanomaterials with specific properties are obtained
Cluster and nanoparticle characterization is
becoming technologically possible and opens new
possibilities in the developments of materials which
could improve the physical and chemical properties
New nanocompounds that could be useful in a
broader way than their bulk counterparts might be
created
Nanotechnology 2
Nanotechnology has experienced
a rapid growth recently because
nanoparticles exhibit physical
and chemical properties that are
quite different from those of the
bulk solid
Nanotechnology 3
The field of nanotechnology
continues to advance at a
breathtaking pace, propelled by
the discovery of new material,
new
devices,
and
new
phenomena.
Nano-scale matter
Nature:
- Novel and emergent phenomena
- Reduced time and time scale
- No merely scale down
CMDCM, Sao Carlos
NANOARTE
http://br.youtube.com
R.Feynman
Richard Feynman’s visionary lecture,
‘‘There is Plenty of Room at the American Physical
Society meeting at Caltech on December 29th 1959, is
often quoted as giving birth to the concept of
nanotechnology: controlling matter at the nanometer
length-scale. It is a highly readable, but remarkably
prescient account of the promise of nanoscience and
technology and well worth reading. There is plenty of
room at the bottom”
http://www.its.caltech.edu/feynman/plenty.html
R.Feynman
The key point of the talk is that the nanoscale is
small enough for extreme minimization, but large
enough (hence ‘‘there is plenty of room’’) to
accommodate sufficient atoms to produce
interesting complexity, if we could just learn how to
control it. Nanotechnology also opens a new
playground for scientists, a terra incognita with
enormous possibilities, and there is plenty of room
for multitudes of scientists to stretch their
imaginations.
“There is plenty of room at the bottom”.
R. P. Feynman, Eng. Sci. 1960, 23, 22.
No doubt, we can add “still” and “tremendous”.
Small is different
Shape-, Size-, and CompositionDependent Properties of Some
Colloidal Semiconductor
Nanocrystals
As the size of material becomes
equal to or falls below the
nanometer length scale that
characterizes the motion of its
electrons
and
thus
its
properties, the latter become
sensitive not only to the size but
also
to
the
shape
and
composition of the particles.
M.A. El-Sayed Acc. Chem. Res. (2004)
“The behavior of large and complex
aggregates of elementary particles, it turns
out, is not to be understood in terms of a
simple extrapolation of the properties of a
few particles. Instead, at each level of
complexity entirely new properties appear,
and the undestanding of the new behaviors
requires research which I think is a
fundamental in its nature as any other”
P. W. Andersson
“At each stage entirely new laws, concepts,
and generalizations are necessary, requiring
inspiration and creativity to just as great a
degree as in the previous one”
P. W. Andersson
Nanomaterials, nanostructures, nanostructured materials,
nanoimprint,
nanobiotechnology,
nanophysics,
nanochemistry, radical nanotechnology, nanosciences,
nanooptics, nanoelectronics, nanorobotics, nanosoldiers,
nanomedecine, nanoeconomy, nanobusiness, nanolawyer,
nanoethics to name a few of the nanos.
We need a clear definition of all these burgeoning fields for
the sake of the grant attribution, for the sake of research
program definition, and to avoid everyone being lost in so
many nanos.
To be nano or not to be nano?
C. Joachim, Nature Materials, 4, 107 (2005)
Over the last few decades, the field of nanotechnology has
grown from a laboratory novelty into a burgeoning industry.
This is a direct result of the new phenomena that are
exhibited a conventional materials are confined to
dimensions less than a few hundred nanometers.
Quantum confinement is another unique property that
exists only in the nanoscale size regime.
Quantum confinement occurs in semiconductors when
their size is restricted to dimensions less than or equal to
the bulk Bohr diameter of an exciton (a bound electron and
hole pair) in that material.
Brus, L. E. J. Chem. Phys. 1984, 80, 4403-4408.
Steigerwald, M. L.; Brus, L. E. Acc. Chem. Res. 1990, 23, 183-188.
When a photon with energy equal to or greater than
the band gap energy is absorbed by a
semiconductor
nanocrystal,
the
resultant
photogenerated electron and hole pair are confined
within the crystal lattice at a distance less than the
thermodynamic quilibrium distance in the same
bulk semiconductor, which can be approximated by
the exciton bulk Bohr diameter.
Much like the ‘particle in a box’
approximation, as a nanocrystal’s diameter
decreases the band gap energy increases
due to the increased confinement.
This energetic size dependence allows the
tuning of the band gap related absorption
and emission simply by changing the
diameter of the nanocrystal.
Kippeny, T. C.; Swafford, L. A.; Rosenthal, S. J.
J. Chem. Ed. 2002, 79, 1094-1100.
Nanoscience,
nanotechnology,
nanoparticles
and
nanostructures are among the most widely used terms in the
modern scientific and technological literature.
The field of nanoscience and nanotechnology (NST) is growing
very rapidly. NST are believed to lead to dramatic modifications of
many of our activities: technologies of information and
communication, medicine, materials, space, energy, water, etc.
Although many fundamental aspects remain to be studied, it is
often claimed that NST should be introduced in the curricula of
scientists and engineers.
When looking at those curricula, it turns out that some
fundamental aspects might be taught in various lectures. Indeed, NST
include elements of mechanics, termodynamics, electricity, quantum
mechanics, etc. Scaling laws may be used to understand the
differences between the macro-, micro- and nanoworlds.
As defined by the Royal Society: nanoscience
is the study of phenomena and manipulation of
materials at atomic, molecular and macromolecular
scales, where properties differ significantly from
those at the larger scale. Nanotechnologies are the
design, characterization, production and application
of structures, devices and systems by controlling
shape and size at the nanometre scale.
The properties of materials can be different at
the nanoscale for two main reasons.
First, nanomaterials have a relatively large
surface area when compared to the same mass
of material produced in a larger form. This can
make materials more chemically reactive (in
some cases materials that are inert in their
larger form are reactive when produced in their
nanoscale form), and affect their strength or
electrical properties.
Second, quantum effects can begin to dominate
the behaviour of matter at the nanoscale particularly
at the lower end affecting the optical, electrical and
magnetic behaviour of materials.
Materials can be produced that are nanoscale
in one dimension (for instance, very thin surface
coatings), in two dimensions (for example,
nanowires and nanotubes) or in all three
dimensions (for example, nanoparticles).
Whilst
recent
developments
in
nanotechnologies and nanosciences have raised
high hopes for a potential new industrial
revolution [1], they have at the same time raised
a number of safety, ethical, policy and regulatory
questions [2,3]. With over one thousand nanoenabled consumer products reported to be
already available globally [4], …
… and many more in the R&D pipeline, it may
seem strange that discussions are still going on
to agree on a common definition of a
nanomaterial that can be used by the producers,
the users, and the regulators alike. Although a
number of definitions are currently available, a
practicable and unambiguous definition of a
nanomaterial is yet to emerge.
It is known that the conventional physicochemical
rules may not be fully applicable at the nanoscale, and may be different from those of bulk
equivalents. Such ‘nano’- related features of
nanomaterials (ENMs) derive from a number of
parameters, such as size, shape, specific surface
area, surface chemistry, etc.
Where a definition has legal consequences,
legislators prefer a simple and clear-cut
distinction, i.e. what is legislated or authorised
and what is not.
A quick glance at the existing definitions of
nanomaterials (Table 1) shows that there is a
virtual consensus on that a nanomaterial is a
material, which is intentionally produced in the
nano-scale (i.e. approximately 1—100 nm), to
have a specific property or a composition.
The 100nm size boundary used in these
definitions, however, only loosely refers to the
nano-scale around which the properties of
materials are likely to change significantly from
conventional equivalents
In reality, there is no clear size cut-off for this
phenomenon, and the 100nm boundary appears
to have no solid scientific basis. A change in
properties of particulate materials in relation to
particle size is essentially a continuum, which
although more likely to happen below 100nm
size range, does not preclude this happening for
some materials at sizes above 100 nm.
Modelling
‘Can I believe modelling?’…
is a question often asked by both
experiment and theoretical researchers. Answering it requires
informed understanding of the strengths and limitations of current
computational molecular modelling and simulation methods, and
their ranges of application.
Knee-jerk scepticism of all modelling is sometimes encountered
among experimentalists even today; equally misguided is a blind
acceptance of modelling results without critical analysis. However,
demonstrations of the practical contribution made by molecular
modelling have led to a growing recognition of its worth. This is a
fertile and growing area, with exciting opportunities and an
enormous range of potential applications. It is crucial for the
molecular modeller to understand the issues of interest to
experimentalists, the complexity of chemical systems and how to
tackle them effectively by modelling.
On the accuracy of modelling and calculations
We break modelling down into four broad categories:
quantum mechanical,
molecular mechanical,
mesoscale,
and bulk scale.
Figure shows roughly the size of systems that are modelled
in each domain and the length of time for which a dynamic
process can be simulated. Generally speaking, as one
moves to larger systems, more approximations are
employed and the methods are less precise.
On the accuracy of modelling and calculations
G. Fitzgerald et al. Materials Modeling from Quantum Mechanics to the Mesoscale
CMES, vol.24, no.3, pp.169-183, 2008
Time
Bulk Scale
Finite element
Seconds
Mesoscale
analysis
Microseconds
Molecular
Self-organized nanostructure
Nanoseconds
Picoseconds
Quantum
Molecular structure of polymer
Electronic structure of methane
Femtoseconds
Distance
1nm
10nm
100nm
1microm
On the accuracy of modelling and calculations
However, even with present-day computers and algorithms, we cannot solve
the many particle Schrödinger equation exactly; inevitably some error is
introduced in approximating the solutions of this equation. Thus, the
accuracy of quantum chemical calculations is of critical importance.
F. Neese, A. Hansen, F. Wennmohs, and S. Grimm
Accurate Theoretical Chemistry with Coupled Pair Models
Acc. Chem. Res., 42, 641-648, 2009.
On the accuracy of modelling and calculations
The affordable accuracy depends on molecular size and particularly
on the total number of atoms: for orientation, ethanol has 9 atoms, aspirin
21 atoms, morphine 40 atoms, sildenafil 63 atoms, paclitaxel 113 atoms,
insulin nearly 800 atoms, and quaternary hemoglobin almost 12000
atoms.
Currently, molecules with up to 10 atoms can be very accurately
studied by coupled cluster (CC) theory, 100 atoms with second-order
Møller-Plesset perturbation theory (MP2), 1000 atoms with density
functional theory (DFT), and beyond that number with semiempirical
quantum chemistry and force-field methods. The overwhelming majority of
present-day calculations in the 100-atom range use DFT.
Dealing with nanomaterials is a challenge for both, experiments
and theory.
Hence, our goal was to combine both approaches to elucidate and
predict their physical and chemical properties, ranging from
optical properties, such as photoluminescence (chapter 7), . growth
mechanism of nanomaterials (chapter 8), simple and complex
metal oxides. (chapter 9), as well as nanocatalysis (chapter 10)
Breakthroughs will continue to emerge when applications of
visualization methods extend into systems of thousands of atoms and
cells, and when the pertinent concepts are generalized with the help of
“simple, but not too simple” theories.
Computations should be considered as tools, keeping in mind that
largescale computations without a “final” theoretical condensate (or better
yet, a “simple equation”) are like large-scale experiments which produce
numerous results that do not boil down to a meaningful finding.
From both experimental and theoretical studies, the ultimate goal is
to provide an understanding of the function from knowledge of structure
and dynamics on different length and time scales. It would be naive to
ignore the evolution of dynamics on these different scales, beginning with
atomic motions, just as ignoring the “big bang” would be misleading for
an understanding of the evolution of planets in the cosmic network.
In the end, we may or may not find that the whole is greater than the
sum of its parts, and learn why nature has designed unique, classical
functions in the quantum world of atoms and molecules.
Raphael’s School of Athens. Exactly five centuries ago, between 1510 and
1511, Raphael captured in his painting the intellectual discourse of
philosophers most probably thinking about the fundamentals of nature.
Natural philosophy, the fundamental science of today, remarkably
emphasized, in the quest for knowledge, dialogue of civilizations,
regardless of origin, faith or gender.
Shown in the painting, among others, are Plato, Aristotle, Ptolemy, Hypatia
of Alexandria, Pythagoras, Alexander the Great, Saladin, and Euclid
(Archimedes).
Note also the beauty of the place where the discourse was held, especially
when compared with many of the present-day university buildings.
The Next Decade of Nanoscience and Nanotechnology
D. Bonnell, ACS Nano, 4, 6293 (2010)
This review reveals that the past decade has indeed seen transformative
changes in the scientific landscape due to nanoscience and nanotechnology
advances. A reminder of the changes would include the following:
● Although plasmons have been around for decades, the ability to exploit
them in nanostructures led to the burgeoning new field of plasmonics, which
did not exist 10 years ago and is producing new technologies.
● After many years of new physics and innovative device configurations
arising from the study of fullerenes and nanotubes, graphene exploded onto
the scene and may enable the realization of the carbon-based systems. That
the Nobel Prize in Physics recognized this new field this year is an indication
of the significance of these advances (see Dresselhaus, M. S.; Araú jo, P. T.
The 2010 Nobel Prize in Physics for Graphene: Some Perspectives. ACS
Nano, 4, 6297 (2010))
● Combinations of near-field optical physics and biochemistry are producing
gene sequencing solutions that may soon meet the $1000/genome challenge
and are enabling single-molecule tracking in dynamic systems such as motor
proteins.
● New families of hybrid materials/structures are being discovered that
exhibit multifunctional behavior, such as multiferroics, spin torque systems,
plasma-induced electronics, and bio-optoelectronics. (see Weiss, P. S.
Combining Function. ACS Nano 2010, 4, 3535 (2010).
● Though local probes of atomic- and molecular-scale structure have been
around for more than a decade, the last 10 years have seen dramatic
extensions to imaging complexity and function at atomic levels. Advances
such as nano nuclear magnetic resonance, spin excitation, and dielectric
function portend a generational leap in our ability to understand nanoscale
phenomena. Note that the 2010 Kavli Prize in Nanoscience acknowledged
this.
● The new field of nanotoxicology and environmental health and safety is
developing the scientific underpinning and social framework for responsible
nanotechnology development (see ACS Nano’s Virtual Issue on
nanotoxicology, http://pubs.acs.org/page/ancac3/vi/1)
Multiscale modelling can be defined as the concurrent study of the different
time and length scales relevant for complex chemical, physical or biological
processes. While this concept is already used in many areas of physics and
material science (e.g. engineering, fluids, and aerodynamics), its realization
in physical chemistry and chemical physics is still relatively new.
Within these disciplines, a multiscale approach connects the established
fields of quantum chemistry, classical molecular dynamics, computational
materials science, and bioinformatics. The importance of such an integral
view for important processes such as photosynthesis, protein folding, DNA
replication, catalysis, etc. is evident.
With the theoretical models in the above-mentioned fields reaching maturity,
complex simulation workflows are emerging that link quantum mechanical
(QM), molecular mechanics (MM), coarse-grained (CG), and continuum
descriptions. The focus is thereby changed from the improvement of
individual components of a workflow, calculations at a single length and/or
time scale, to the improvement of the complete model and the transfer of
information between the levels.
Feeding the larger length scale simulations with ab initio parameters from
lower length scales requires a thorough matching of the physics in the two
models and efficient implementation of the entire workflow.
As multiscale modelling developments are primarily discussed in the
literature of the parent fields, cross-fertilization between the different fields is
still limited. This themed issue, collecting ideas on multiscale modelling
across the broad field of physical chemistry and chemical physics, therefore
aims to enhance the interdisciplinary exchange of ideas.
The future is hard to predict. Yet, it is almost certain that in the coming
decades new multiscale modelling methods, comprising quantum chemistry,
classical MD, static and dynamic coarse graining, multi-level and hybrid
simulations in all their forms will continue to be developed, allowing
researchers in the field of physical chemistry and chemical physics to access
ever more complex systems on larger length and time scales, without loosing
essential microscopic features.
Multiscale modelling
L. Visscher, P. Bolhuis, and F. M. Bickelhaupt,
Phys. Chem. Chem. Phys., 2011, 13, 10399.
Read
Nano-Age. How Nanotechnology Changes our Future.
By Mario Pagliaro. Wiley-VCH, Weinheim 2010.
This book attempts to answer such questions. It is a perspective about the
impact (past, present, and possibly future) of nanotechnology in society
Read
The long view of nanotechnology development: the National Nanotechnology
Initiative at 10 years
M. C. Roco, J Nanopart Res (2011) 13:427–445
Read
Nano-Age. How Nanotechnology Changes our Future.
By Mario Pagliaro. Wiley-VCH, Weinheim 2010.
This book attempts to answer such questions. It is a perspective about the
impact (past, present, and possibly future) of nanotechnology in society
Read
From Ideas to Innovation: Nanochemistry as a Case Study
G. A. Ozin and L. Cademartiri, Small 2010, DOI: 10.1002/smll.201001097
Read
Quantum well structures in thin metal films: simple model physics in reality?
M Milun, P Pervan and D P Woodruff
Rep. Prog. Phys. 65 (2002) 99–141
Read
Van Hove Singularities as a Result of Quantum Confinement: The
Origin of Intriguing Physical Properties in Pb Thin Films
Y. J. Sun, S. Souma, W.J. Li, T. Sato, X. G. Zhu, G. Wang, X. Chen, X. C.
Ma, Q. K. Xue, J. F. Jia, T. Takahashi, and T. Sakurai
Nano Res. 2010, 3(11): 800–806
Read
The devil is in the details (or the surface): impact of surface structure and
surface energetics on understanding the behavior of nanomaterials in the
Environment.
I. A. Mudunkotuwa and V. H. Grassian, J. Environ. Monit., 2011, 13, 1135
Read
Nanosensors: Does Crystal Shape Matter?
A. Gurlo, Small 2010, 6, No. 19, 2077–2079
Read
Nanotechnology Regulation: A Study in Claims Making
T.F. Malloy, ACS Nano, 5, 5-12 (2011)