Supporting information: The role of intra-molecular dynamics on intermolecular coupling in J-aggregates
T.Virgili*1, L. Lüer2, G. Lanzani3, G. Cerullo2, S. Stagira2, D. Coles4, A. J. H. M. Meijer5 &
D. G. Lidzey*4
1
2
Istituto di Fotonica e Nanotecnologie-CNR, Piazza L. da Vinci, 32, 20133 Milano, Italy
ULTRAS – INFM-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo Da Vinci
32, 20133 Milano, Italy
3
CNST, IIT@POLIMI, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo Da Vinci
32, 20133 Milano, Italy
4
Department of Physics and Astronomy, University of Sheffield, Hicks Building, Hounsfield Road,
Sheffield S3 7RH United Kingdom
5
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF United Kingdom
Supplementary Method 1
The calculation of the NK-2707 Raman modes were performed using the SMP version of
the Gaussian 03 [1] program package with the B3LYP functional method [2]. Gaussian was
compiled using the Portland Compiler version 7.0-5 with the GOTO implementation (v.1.26) of
BLAS [3] on the EMT64 architecture. In all preliminary calculations the 6-31G** basis was used
on all atoms [4]. Calculations were run for the bare anion, its corresponding acid and on the entire
ionic complex. For each of these we used various starting geometries. The resultant lowest energy
conformers were subsequently used in frequency calculations to obtain the harmonic vibrational
frequencies, IR intensities and Raman activities. It is well-known that B3LYP overestimates the
calculated frequencies, an thus the frequencies were scaled by 0.98 to compensate for this. Some
initial analysis on these calculations was performed using the GaussSum programme. The Raman
activities were transformed into intensities using the expression [5]:
C   0  Si
4
R
i
I =

 hc i
 i 1  exp  
 kT




.
(1)
Unlike in Ref. [5] it was found that the Boltzmann term [1-exp(-hci/kT)] in the denominator of Eq.
1 does not overemphasize the low energy modes in the solid state, and this was needed to obtain a
reasonable agreement with experiment. Therefore, the influence of vibrationally excited states on
the Raman signal is included. From the Raman intensities we subsequently generated spectra by
broadening each of the Raman lines with a lorentzian of width 3 cm-1 using in-house developed
software, which were compared to experiment.
Our calculations demonstrated that the bare anion showed the best agreement with
experiment. Therefore, this calculation was re-run using the 6-311G** basis set [6]. Again, a
scaling of 0.98 was used to obtain the best agreement with experiment. This final calculation on
C24H23Cl2N2O6S4- contained 870 basis functions and 328 electrons.
References:
[1] Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam,
S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C.
Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V.
G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck,
K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A.
Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M.
W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2003.
[2] A. D. Becke, Density-functional thermochemistry. III. The role of exact exchange J. Chem.
Phys. 98, 5648, (1993)
[3] Kazushige Goto and Robert A. van de Geijn, Anatomy of a High-Performance Matrix
Multiplication ACM Transactions on Mathematical Software, 34 Article 12 (2008)
[4] M. M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, D. J. DeFrees, J. A. Pople, and M. S.
Gordon, Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for secondrow elements J. Chem. Phys. 77, 3654 (1982)
[5] D. Michalska and R. Wysokinski, The prediction of Raman spectra of platinum(II) anticancer
drugs by density functional theory Chem. Phys. Lett. 403, 211 (2005)
[6] A. D. McLean and G. S. Chandler, Contracted Gaussian basis sets for molecular calculations. I.
Second row atoms, Z=11–18 J. Chem. Phys. 72, 5639 (1980)
Supplementary Method 2
Supplementary information Calculations
Figure 1: Minimum energy structure anion calculated using density functional theory utilizing the B3LYP functional and a 6311G** basis set.
Coordinates for structure in Figure 1:
61
C
C
C
C
C
C
C
H
H
C
C
H
C
H
C
C
C
-4.71734
-4.53116
-5.59232
-6.86952
-7.04475
-5.99556
-2.41452
-5.43546
-6.18895
-1.14490
0.09618
-1.12299
1.20063
1.03121
2.49805
4.59122
4.77069
-0.84722
-1.17719
-1.56225
-1.62574
-1.30289
-0.91000
-0.54385
-1.80212
-0.64354
-0.19320
-0.26394
0.27130
0.28205
0.60019
0.47387
0.96313
0.94965
-0.01012
-1.35849
-2.16496
-1.61619
-0.27255
0.54772
-0.16712
-3.20933
1.57543
0.27778
-0.38146
1.25354
0.28376
1.30477
-0.19450
-1.48614
-0.09720
C
C
C
H
C
H
C
C
H
H
H
H
C
C
H
H
H
H
C
H
H
C
H
H
N
N
Cl
Cl
S
S
C
H
H
H
S
O
O
O
S
O
O
O
H
H
5.65567
6.03236
6.91584
5.51261
7.08056
6.20871
3.60885
4.16048
2.59713
4.20938
4.25168
5.17183
-3.47430
-3.38455
-2.61776
-4.36124
-3.37456
-2.43154
-4.49172
-4.64227
-5.45074
3.32688
2.25642
3.48195
-3.52774
3.59123
8.68167
-8.66434
2.91576
-2.84591
0.27262
-0.43377
0.10626
1.27336
3.81750
5.29460
3.09213
3.35472
-4.06072
-2.72004
-4.03993
-5.15005
7.76387
-7.71819
1.19838
1.18700
1.44155
1.19145
1.43464
1.16311
0.46590
-0.89742
0.60481
1.26925
-0.82269
-1.05280
-0.15225
1.34678
-0.67566
-0.58490
1.38850
1.76650
2.25916
3.09715
1.75433
-2.13671
-1.93112
-2.90523
-0.52056
0.69494
1.74289
-1.39067
0.67263
-1.02827
-0.98743
-1.81396
-0.32508
-1.41974
-2.96986
-3.05844
-4.25521
-2.05589
3.05343
3.63900
1.93658
4.03022
1.62664
-1.91395
-2.34643
0.45090
-1.80935
-3.41974
-0.42516
1.51568
2.05127
2.49588
2.42535
2.48600
3.58668
2.11000
2.05477
2.38438
2.48796
2.51780
3.48101
2.05263
1.84553
2.52696
1.71342
2.14649
2.08447
2.90452
0.63152
0.59646
0.24295
0.41948
-1.88726
-1.80110
-1.69082
-1.77132
-2.54755
-1.74823
0.57525
0.67123
0.62484
-0.51522
0.23535
0.49317
-0.75015
0.02921
-2.45434
-2.22110
Supplementary Movies
These movies show the calculated vibrational motion of the NK-2707 undergoing coherent
vibrational motion around a frequency of 318 (movie318.mpg) and 609 cm-1 (movie609.mpg).