1
Supplemental Material
for
Interpretation of the vacuum ultraviolet photoabsorption
spectrum of iodobenzene by ab initio computations
Michael H. Palmer,1a Trevor Ridley,1 Søren Vrønning Hoffmann,2 Nykola C. Jones,2 Marcello
Coreno,3 Monica de Simone,4 Cesare Grazioli,4,5 Malgorzata Biczysko,6,7 Alberto Baiardi,6,7
and Paulo Limão-Vieira8
1
School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road,
Edinburgh EH9 3FJ, Scotland, UK
2
ISA,Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000
Aarhus C, Denmark
3
CNR-ISM, Montelibretti, c/o Laboratorio Elettra, Trieste, Italy
4
CNR-IOM Laboratorio TASC, Trieste, Italy
5
Department of Chemical and Pharmaceutical Sciences, University of Trieste, Italy
6
National Research Council ICCOM-CNR, UOS di Pisa, Via G. Moruzzi 1, I-56124 Pisa, Italy
7
Scuola Normale Superiore, Piazza Cavalieri 7, 56126 Pisa, Italy
8
Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física,
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica,
Portugal
Email:
m.h.palmer@ed.ac.uk;
marcello.coreno@elettra.eu;
vronning@phys.au.dk;
desimone@iom.cnr.it;
nykj@phys.au.dk;
malgorzata.biczysko@sns.it;
plimaovieira@fct.unl.pt
a
Phone: +44 (0) 131 650 4822
Contents:
SM1. Singlet state equilibrium structures ............................................................................ 2
SM2. Further details of the MRD-CI vertical excitation to singlet states .......................... 3
SM3. Logarithmic plot of the calculated oscillator strengths for valence states………….5
SM4. Interpretation of the 6 to 6.9 eV region of the VUV spectrum .................................. 5
=================================================================
SM1. Singlet state equilibrium structures
2
Figure S1
Excited state equilibrium structures of PhI
3
SM2. Further details of the MRD-CI vertical excitation to singlet states
Energy
/ eVa
0.000
4.770
5.088
5.677
5.743
6.206
6.386
6.511
6.631
6.787
6.794
6.874
6.938
7.052
7.166
7.185
7.258
7.329
7.455
7.567
7.723
7.777
7.998
8.207
8.392
8.545
8.546
8.583
8.677
8.750
8.756
8.760
8.776
8.803
8.980
8.985
9.109
9.133
9.202
9.223
9.235
9.289
Oscillator Symmetry
strength
106f(r)
1
0
A1
1
4708
B2
1
10751
B1
1
380670
A1
1
10997
B2
1
13343
A1
1
166706
B2
1
1019
A1
1
0
A2
1
34858
B1
1
2642
A1
1
0
A2
1
72747
B2
1
15
A1
1
42
A1
1
2269
B1
1
799397
A1
1
666276
B2
1
46165
A1
1
170257
A1
1
307
A1
1
0
A2
1
0
A2
1
4917
B1
1
2958
B1
1
34959
B1
1
18000
B1
1
5244
B1
1
0
A2
1
0
A2
1
0
A2
1
217
B2
1
49
A1
1
13523
B1
1
1313
B2
1
401
A1
1
105286
A1
1
50892
B2
1
10677
B1
1
0
A2
1
0
A2
1
68908
B1
Leading terms in decreasing
density.
valence shell numbering
X1A1
3b12a2*;1a24,5b1
3b19a1*
3b14b1*
6b29,11a1*
3b16b1*
3,2b12a2* + 1a24,5b1
8a112a1*
1a29,11,10a1*
2b19,10,11a1*
3b15b1*
6b24,5b1*
6b210,9a1*
2b14b1*
6b28b2*
6b22a2*
1a22a2*
2b12a2* -1a24b1*
6b27b2*
8a111a1*
3b104b12* (#)
1a212,10,11a1*
3b17b2*
3b111a1*
7a14,5b1*; 3b111a1*
1a27,9b2*
7a14,5b1*
5b22a2*
5b24,5b1*
6b25,4b1*
8,7a12a2*
1a26b1; + 2b12a2*
3b16b29a1*2a2* (#)
2b1 11,13a1*; 7a14b1*
6b211,9a1*
3b17b1*
8a110a1*
1a24,5b1*-2b11a2*
2b110,9a1*; 3b112a1*
3b19,8b2*
1a210,12,11a1*
3b113,12a1*; 2b110a1*
Second moments of the
charge distribution
<x2>
<y2>
<z2>
-51.4 -44.1 -42.8
-52.0 -46.0 -43.3
-50.7 -46.2 -43.4
-53.2 -47.1 -45.6
-52.2 -43.3 -49.4
-58.9 -47.1 -49.1
-51.8 -47.8 -49.2
-53.4 -53.9 -78.4
-51.8 -42.8 -45.8
-53.7 -48.6 -41.9
-72.7 -49.2 -47.3
-54.7 -45.7 -51.0
-63.1 -51.4 -55.1
-58.2 -47.4 -44.5
-54.7 -60.7 -59.5
-53.3 -47.1 -50.0
-56.5 -45.8 -44.3
-57.4 -47.6 -44.6
-59.2 -64.8 -49.0
-57.0 -45.9 -42.4
-58.3 -48.5 -46.9
-53.9 -53.7 -61.6
-56.6 -68.9 -45.4
-59.7 -49.0 -67.9
-55.7 -46.5 -52.4
-54.5 -65.3 -37.3
-56.9 -47.0 -55.1
-53.9 -42.4 -41.8
-56.1 -41.1 -43.2
-76.2 -47.5 -49.9
-53.7 -46.7 -41.8
-54.5 -45.2 -48.0
-53.1 -46.1 -53.4
-58.7 -49.3 -57.9
-63.0 -47.1 -64.9
-54.0 -46.8 -49.5
-62.5 -51.5 -41.4
-70.3 -46.4 -44.3
-57.3 -50.7 -62.6
-51.8 -62.4 -42.5
-61.6 -49.4 -50.2
-53.0 -49.2 -83.6
4
9.366
9.368
9.376
9.462
9.468
9.652
9.764
9.793
9.874
9.901
10.080
10.098
10.306
10.308
10.334
10.356
10.356
10.384
10.420
10.462
10.545
10.577
10.629
10.639
10.656
10.660
10.710
10.711
10.954
Footnotes
a
b
22108
0
0
0
979
1220
43709
0
9585
0
9306
8798
23633
308623
8516
56639
0
0
12524
108933
3853
4954
0
0
3902
7618
1873
920
1360
1
B2
A2
1
A2
1
A2
1
B2
1
B1
1
B1
1
A2
1
B2
1
A2
1
B2
1
B1
1
B2
1
A1
1
B1
1
B2
1
A2
1
A2
1
B2
1
A1
1
A1
1
B2
1
A2
1
A2
1
B2
1
B1
1
B2
1
B1
1
B1
1
6b214a1*
3b18b2*
7,8a12a2*
1a211,9,10a1*
5b29,11a1*
3b113,12a1*; 2b110a1*
2b112,13a1*; 3b112a1*
3b16b29a12*
6b212,13a1*
1a213a1*
1b12a2*+ 1a25b1*
7a14b1*; 2b111,13a1*
5b212,10a1*
6b29b2*
1b19a1*
8a17b2*
2b17b2*
1a215a1*
6b214a1* + 1a27b1
8a19a1*
1b14b1*
3b13a2*
2b13b18b22*
1a214a1*
5b210,12a1*
8a15,4b1*
6b213a1*
1a29,7b2*
2b113,12,11a1*
-53.9
-51.5
-53.6
-58.5
-55.1
-54.0
-51.2
-54.9
-53.4
-53.3
-52.5
-55.0
-57.8
-52.3
-52.7
-59.0
-56.2
-55.3
-55.4
-59.3
-54.1
-57.9
-50.8
-52.2
-59.4
-77.1
-53.0
-53.8
-51.1
-54.5
-63.2
-48.9
-45.6
-40.5
-64.4
-63.9
-46.4
-57.0
-52.5
-46.9
-50.8
-47.5
-58.2
-44.5
-67.5
-68.5
-46.0
-51.1
-49.8
-51.9
-52.5
-67.9
-59.3
-48.7
-48.3
-57.4
-56.9
-51.9
-61.4
-64.7
-36.5
-69.7
-48.8
-45.0
-62.4
-69.0
-77.2
-68.1
-46.5
-50.4
-63.7
-63.0
-51.2
-45.9
-44.8
-62.9
-57.8
-71.1
-48.7
-41.7
-66.1
-60.9
-55.7
-45.1
-67.8
-60.3
-84.7
X1A1 ground state CI energy -7148.87243 a.u.
Terms such as the following (at energy 4.770 eV) 3b12a2*;1a24,5b1 show a singlet state with
three leading terms; the first is the dominant one, whereas the second term 1a24,5b1 shows two
further excitations involving the 1a2 orbital, with excitations into 4b1* and 5b1* in decreasing
densities. A further explanation relates to terms such as that at 6.386 eV (3,2b12a2* + 1a24,5b1);
this involves 4 leading terms; two excitations are from the occupied MOs 3b1 and 2b1 into 2a2*,
and two from 1a2 into two virtual molecular orbitals (VMOs). Excitations into a1* and b2*
orbitals especially, often show the highest density terms occur with several VMOs; an example
with energy 7.777 eV marked as 1a212,10,11a1* shows three leading terms where the three a1*
MOs have highest density in 12a1* and lowest in 11a1*. Doubly excited states are marked (#).
Linear combinations of leading terms are marked symmetric (+) and antisymmetric(-).
5
SM3. Logarithmic plot of the calculated oscillator strengths for valence states
Figure S2.
The experimental VUV absorption spectrum of PhI, (black) with superimposed
all-electron MRD-CI vertical energies and a logarithmic plot of the calculated oscillator
strengths for valence states (red) which emphasizes the variation in f(r).
SM4. Interpretation of the 6 to 6.9 eV region of the VUV spectrum
The 6.0 to 6.9 eV band is shown in Fig. S3. The most intense component bands (eV,
f(r)), using uncorrected energies are: 1B1 (6.182, 0.055), 1B1 (6.287, 0.031), 1A1 (6.555, 0.242)
and 1B2 (6.916, 0.035). Attempts to determine several additional equilibrium structures were
frustrated by state swapping between TDDFT iterations; the state sequence is often very
sensitive to small geometric changes.
6
Figure S3.
The 6 to 6.9 eV region is dominated by ππ* states, but the present study suggests
that distortion of the ring from C2v to CS symmetry may occur as well.