Nonadiabatic mixed quantum-classical dynamic simulation of π-stacked oligophenylenevinylenes

Journal of Physical Chemistry A

Volumn 113, Issue 15, 2009, Pages 3427-3430

  Sterpone, Fabio ^a   Bedard Hearn, Michael J ^b   Rossky, Peter J ^b  

^a ECOLE NORMALE SUPÉRIEURE   (France)

^b UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BOUND EXCITONS; CHARACTERISTIC TIME; CONFIGURATION INTERACTIONS; ELECTRONIC ABSORPTION SPECTRUM; ELECTRONIC HAMILTONIANS; MIXED QUANTUM-CLASSICAL DYNAMICS; NA TRANSITIONS; NON EQUILIBRIUMS; NON-ADIABATIC; OLIGOPHENYLENEVINYLENES; ONE CHAINS; QUANTUM-CLASSICAL MOLECULAR DYNAMICS SIMULATIONS; RADIATIVE COUPLINGS; RAPID TRANSITIONS; SLIDING MOTIONS; THERMAL MOTIONS; TIGHT-BINDING APPROXIMATIONS;

ABSORPTION SPECTROSCOPY; ELECTRIC EXCITATION; ELECTRONIC STRUCTURE; GROUND STATE; MOLECULAR DYNAMICS; PHOTOEXCITATION; POLYMERS; QUANTUM ELECTRONICS;

DYNAMICS;

EID: 64849111850     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp901229z     Document Type: Article

References (31)

1. Schwartz. B. J. Annu. Rev. Phys. Chem. 2003, 54, 141.
2. Brédas, J.-L.; Beljonne, D.; Coropceanu, V.; Cornil, J. Chem. Rev. 2004, 104, 4971.
3. Cornil, J.: Heeger, A. J.; Brédas, J.-L. Chem. Phys. Lett. 1997, 272, 463-470.
4. Cornil, J.; dos Santos. D. A.; Crispin, X.: Silbev, R.; Brédas, J.-L. J. Am. Chem. Soc. 1998, 120, 1289.
5. Tretiak, S.; Saxena, A.: Martin. R. L.: Bishop, A. R. J. Phys. Chem. B 2000, 104, 7029.
6. Hutchison, G. R.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 16866-16881.
7. Brédas, J.-L.: Cornil, J.; Beljonne, D.: dos Santos, D. A.; Shuai, Z. Acc. Chem. Res. 1999, 32, 267.
8. Lobaugh, J.: Rossky. P. J. J. Phys. Chem. A 1999, 103, 9432-9447.
9. Lobaugh, J.; Rossky, P. J. J. Phys. Chem. A 2000, 104, 899-907.
10. Sterpone. F.: Rossky, P. J. Phys. Chem. B 2008, 112 (16), 4983.
11. Oelkrug, D.; Tompert, A.; Gierschner, J.; Egelhaaf. H.-J.; Hanack, M.: Hohloch, M.: Steinhuber, E. J. Phys. Chem. B 1998, 102, 1902-1907.
12. Bjorklund, T. G.; Lim. S.-H.: Bardeen, C. J. Synth Met. 2004, 142, 195-200.
13. Pariser, R.; Parr, R. G. J. Chem. Phys. 1953, 21, 466.
14. Pariser, R.; Parr, R. G. J. Chem. Phys. 1953, 21, 767.
15. Pople, J. A. Trans. Faraday Soc. 1953, 49, 1375.
16. Warshel, A.: Karplus, M. J. Am. Chem. Soc. 1972, 94, 5612.
17. Hurley, A. C. Electronic Correlation in Small Molecules: Academic Press: New York, 1976.
18. By increasing the number of SCI states from 50 to 200, the energy gaps changed by only 2-3%. The electronic density of states computed a posteriori using a previously generated trajectory was demostrated to be visibly unchanged.
19. Drukker, K. J. Comput. Phys. 1999, 153, 225.
20. Allen, M. P.; Tildesely, D. J. Computer Simulation of Liquids: Oxford University Press: New York, 1987.
21. Tully, J. C. J. Chem. Phys. 1990, 93, 1061.
22. We use a fourth-order Runge- Kutta algorithm to integrate the time-dependent Schrödinger equation with 1000 intermediate time steps.
23. Only transitions to the first three states are included since the description of higher-lying excited states within the SCI space is likely incomplete.
24. Ruini, A.; Caldas, M. J.; Bussi, G.: Molinari, E. Phys. Rev. Lett. 2002, 88, 2064031.
25. Bussi, G.; Ferretti, A.; Ruini, A.; Caldas, M. J.: Molinari, E. Adv. Solid State Phys. 2003, 43, 313-326.
26. 4. shows some charge-transfer character, as indicated by a substantial interchain transition dipole moment, but as it has no intensity in the GS absorption spectrum, we do not discuss it here.
27. We decompose the vector between the centers of mass into parallel and orthogonal components to describe the sliding dynamics and contact distance, respectively. The parallel direction is chosen to be a unit vector pointing between the first and last carbon atoms on one chain, and the remainder of the joint center-of-mass vector is in the orthogonal direction; other reasonable definitions of these unit vectors yielded similar results.
28. if can spike one or more times prior to making the NA transition since the surface-hopping algorithm used is stochastic (see ref 21).
29. Bjorklund, T.; Lim, S.-H.: Bardeen, C. J. Phys. Chem. B 2001, 105, 11970.
30. Kersting, R.: Lemmer, U.: Mahrt, R. F.: Leo, K.; Kurz, H.; Bässler, H.; Göbel, E. O. Phys. Rev. Lett. 1993, 70, 3820.
31. System renderings made with PyMOL, DeLano, W. L. http://www.pymol.org.