Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
A new glance at HCl-monohydrate spectroscopy, using on-the-fly dynamics
On-the-fly dynamics is used to analyze the remarkably anharmonic infrared spectroscopy of crystalline HCl monohydrate, an ionic solid composed of H3O+ and Cl−. The dominant intense infrared feat...
Next Article
Energy quantization of chaos with the semiclassical phases alone
The mechanism of energy quantization is studied for classical dynamics on a highly anharmonic potential, ranging from integrable, mixed, and chaotic motions. The quantum eigenstates (standing waves) a...

Exciton dissociation at donor-acceptor polymer heterojunctions: Quantum nonadiabatic dynamics and effective-mode analysis

J. Chem. Phys. 126, 021103 (2007); doi:10.1063/1.2431358

Published 11 January 2007

You are not logged in to this journal. Log in

Hiroyuki Tamura
Département de Chimie, Ecole Normale Supérieure, 24 rue Lhomond, F-75231 Paris cedex 05, France

Eric R. Bittner
Department of Chemistry and Texas Center for Superconductivity, University of Houston, Houston, Texas 77204

Irene Burghardt
Département de Chimie, Ecole Normale Supérieure, 24 rue Lhomond, F-75231 Paris cedex 05, France
The quantum-dynamical mechanism of photoinduced subpicosecond exciton dissociation and the concomitant formation of a charge-separated state at a semiconducting polymer heterojunction is elucidated. The analysis is based upon a two-state vibronic coupling Hamiltonian including an explicit 24-mode representation of a phonon bath comprising high-frequency (C[Double Bond]C stretch) and low-frequency (torsional) modes. The initial relaxation behavior is characterized by coherent oscillations, along with the decay through an extended nonadiabatic coupling region. This region is located in the vicinity of a conical intersection hypersurface. A central ingredient of the analysis is a novel effective mode representation, which highlights the role of the low-frequency modes in the nonadiabatic dynamics. Quantum dynamical simulations were carried out using the multiconfiguration time-dependent Hartree method. ©2007 American Institute of Physics
History: Received 26 October 2006; accepted 7 December 2006; published 11 January 2007
Permalink: http://link.aip.org/link/?JCPSA6/126/021103/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (361 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 71.35.-y
    Excitons and related phenomena
  • 71.20.Rv
    Electronic structure of polymers and organic compounds
  • 63.50.+x
    Vibrational states in disordered systems
  • YEAR: 2007

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (32)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. R. H. Friend, R. W. Gymer, A. B. Holmes et al., Nature 397, 121 (1997).
  2. G. D. Scholes and G. Rumbles, Nat. Mater. 5, 683 (2006).
  3. E. R. Bittner and J. G. S. Ramon, in Quantum Dynamics of Complex Molecular Systems, edited by I. Burghardt and D. A. Micha (Springer, Heidelberg, 2006).
  4. J. Ramon and E. R. Bittner, J. Phys. Chem. B 110, 21001 (2006)
  5. E. R. Bittner, J. Ramon, and S. Karabunarliev, J. Chem. Phys. 122, 214719 (2005).
  6. S. Karabunarliev and E. R. Bittner, J. Chem. Phys. 119, 3988 (2003).
  7. S. Karabunarliev and E. R. Bittner, J. Chem. Phys. 118, 4291 (2003).
  8. S. Karabunarliev, E. R. Bittner, and M. Baumgarten, J. Chem. Phys. 114, 5863 (2001).
  9. G. Lanzani, G. Cerullo, C. Brabec, and N. S. Sacriftci, Phys. Rev. Lett. 90, 047402 (2003).
  10. R. Kersting, U. Lemmer, R. F. Mahrt, K. Leo, H. Kurz, H. Bässler, and E. O. Göbel, Phys. Rev. Lett. 70, 3820 (1993).
  11. P. Sreearunothai, A. C. Morteani, I. Avilov, J. Cornil, D. Beljonne, R. H. Friend, R. T. Phillips, C. Silva, and L. M. Herz, Phys. Rev. Lett. 96, 117403 (2006).
  12. J. J. M. Halls, J. Cornil, D. A. dos Santos, R. Silbey, D.-H. Hwang, A. B. Holmes, J. L. Brédas, and R. H. Friend, Phys. Rev. B 60, 5721 (1999).
  13. A. C. Morteani, P. Sreearunothai, L. M. Herz, R. H. Friend, and C. Silva, Phys. Rev. Lett. 92, 247402 (2004).
  14. The exciplex denotation is often taken to imply that intermolecular—i.e., inter-chain—relaxation is accounted for; this is not the case in our model.
  15. A. Pereverzev and E. R. Bittner, J. Chem. Phys. 125, 104906 (2006).
  16. A. C. Morteani, A. S. Dhoot, J.-S. Kim, C. Silva, N. C. Greenham, C. Murphy, E. Moons, S. Cina, J. H. Burroughes, and R. H. Friend, J. Adv. Mater. 15, 1708 (2003).
  17. As a result, the overall photoluminescence efficiency of the TFB:F8BT blend is [approximate]60% that of the pure F8BT, in spite of the presence of a heterojunction.
  18. L. S. Cederbaum, E. Gindensperger, and I. Burghardt, Phys. Rev. Lett. 94, 113003 (2005).
  19. I. Burghardt, E. Gindensperger, and L. S. Cederbaum, Mol. Phys. 104, 1081 (2006).
  20. E. Gindensperger, I. Burghardt, and L. S. Cederbaum, J. Chem. Phys. 124, 144103 (2006).
  21. I. Burghardt, in Quantum Dynamics of Complex Molecular Systems, edited by I. Burghardt and D. A. Micha (Springer, Heidelberg, 2006).
  22. H.-D. Meyer, U. Manthe, and L. S. Cederbaum, Chem. Phys. Lett. 165, 73 (1990).
  23. M. H. Beck, A. Jäckle, G. A. Worth, and H.-D. Meyer, Phys. Rep. 324, 1 (2000).
  24. G. A. Worth, M. H. Beck, A. Jäckle, and H. Meyer, The MCTDH Package, Version 8.2 (2000); H.-D. Meyer, Version 8.3 (2002). See http://www.pci.uni-heidelberg.de/tc/usr/mctdh/
  25. H. Tamura, E. R. Bittner, and I. Burghardt (unpublished).
  26. P. Grigolini and G. P. Parravicini, Phys. Rev. B 25, 5180 (1982).
  27. E. Gindensperger, H. Köppel, and L. S. Cederbaum, J. Chem. Phys. (to be published).
  28. H. Köppel, W. Domcke, and L. S. Cederbaum, Adv. Chem. Phys. 57, 59 (1984).
  29. In particular, the parameters correspond to the vertical SCI energies, gradients, and interstate couplings computed at the ground-state equilibrium configuration of the polymer dimer. The interchain couplings were adjusted to reproduce the spectroscopic estimates of the XT/CT splitting (Ref. 13). The resulting distribution of parameters {kappa<sub>i</sub><sup>(1)</sup>,kappa<sub>i</sub><sup>(2)</sup>,lambdai} is not regular; in general, a few modes tend to dominate within a given branch and coupling type. Further, the off-diagonal couplings {lambdai} tend to be weaker than the diagonal couplings. The band widths covered by the high-frequency (C[Double Bond]C stretch) vs low-frequency (ring-torsional) modes are of about 0.02 and 0.001  eV, respectively. A complete listing of the parameters is available as supplementary material of Ref. 15.
  30. G. J. Atchity, S. S. Xantheas, and K. Ruedenberg, J. Chem. Phys. 95, 1862 (1991).
  31. D. G. Truhlar and C. A. Mead, Phys. Rev. A 68, 032501 (2003).
  32. S. Karabunarliev, M. Baumgarten, E. R. Bittner, and K. Müllen, J. Chem. Phys. 113, 11372 (2000).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics