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Formation and relaxation of excited states in solution: A new time dependent polarizable continuum model based on time dependent density functional theory

Source: J. Chem. Phys. 124, 124520 (2006); doi:10.1063/1.2183309

Published 31 March 2006

KEYWORDS and PACS
Keywords
PACS
  • 61.20.Lc
    Time-dependent properties of liquid structure; relaxation
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • YEAR: 2006
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PUBLICATION DATA
ISSN:
1553-9644 (online)
Publisher:
AIP is a member of CrossRef AIP
Marco Caricato, Benedetta Mennucci, and Jacopo Tomasi
Dipartimento di Chimica, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy

Francesca Ingrosso
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872

Roberto Cammi
Dipartimento di Chimica, Università di Parma, Viale delle Scienze 17/A, 43100 Parma, Italy

Stefano Corni
INFM-CNR Center on nanoStructures and bioSystems at Surfaces (S3), Via Campi 213/A, 41100 Modena, Italy

Giovanni Scalmani
Gaussian, Inc., Wallingford, Connecticut 06492
In this paper a novel approach to study the formation and relaxation of excited states in solution is presented within the integral equation formalism version of the polarizable continuum model. Such an approach uses the excited state relaxed density matrix to correct the time dependent density functional theory excitation energies and it introduces a state-specific solvent response, which can be further generalized within a time dependent formalism. This generalization is based on the use of a complex dielectric permittivity as a function of the frequency, epsilon-hat(omega). The approach is here presented in its theoretical formulation and applied to the various steps involved in the formation and relaxation of electronic excited states in solvated molecules. In particular, vertical excitations (and emissions), as well as time dependent Stokes shift and complete relaxation from vertical excited states back to ground state, can be obtained as different applications of the same theory. Numerical results on two molecular systems are reported to better illustrate the features of the model. ©2006 American Institute of Physics
History: Received 19 December 2005; accepted 10 February 2006; published 31 March 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/124520/1

REFERENCES (31)

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  1. J. Tomasi and M. Persico, Chem. Rev. (Washington, D.C.) 94, 2027 (1994).
  2. C. J. Cramer and D. G. Truhlar, Chem. Rev. (Washington, D.C.) 99, 2161 (1999).
  3. J. Tomasi, B. Mennucci, and R. Cammi, Chem. Rev. (Washington, D.C.) 105, 2999 (2005).
  4. B. Mennucci, R. Cammi, and J. Tomasi, J. Chem. Phys. 109, 2798 (1998).
  5. R. Cammi and B. Mennucci, J. Chem. Phys. 110, 9877 (1999);
    6. R. Cammi, B. Mennucci, and J. Tomasi, J. Phys. Chem. A 104, 5631 (2000).
  6. M. Cossi and V. Barone, J. Chem. Phys. 115, 4708 (2001).
  7. M. V. Basilevskyi, D. F. Parsons, and M. V. Vener, J. Chem. Phys. 108, 1103 (1998).
  8. I. V. Rostov, M. V. Basilevsky, and M. D. Newton, in Simulation and Theory of Electrostatic Interactions in Solution, edited by L. R. Pratt and G. Hummer (American Institute of Physics, New York, 1999).
  9. P. G. Wolynes, J. Chem. Phys. 86, 5133 (1987).
  10. M. D. Newton and H. L. Friedman, J. Chem. Phys. 88, 4460 (1988).
  11. C. P. Hsu, X. Song, and R. A. Marcus, J. Phys. Chem. B 101, 2546 (1997).
  12. F. Ingrosso, B. Mennucci, and J. Tomasi, J. Mol. Liq. 108, 21 (2003).
  13. R. Cammi, S. Corni, B. Mennucci, and J. Tomasi, J. Chem. Phys. 122, 104513 (2005).
  14. S. Corni, R. Cammi, B. Mennucci, and J. Tomasi, J. Chem. Phys. 123, 134512 (2005).
  15. E. Cancès, B. Mennucci, and J. Tomasi, J. Chem. Phys. 107, 3032 (1997);
    16. B. Mennucci, E. Cancès, and J. Tomasi, J. Phys. Chem. B 101, 10506 (1997).
  16. S. Miertus, E. Scrocco, and J. Tomasi, Chem. Phys. 55, 117 (1981);
    17. R. Cammi and J. Tomasi, J. Comput. Chem. 16, 1449 (1995).
  17. M. Caricato, F. Ingrosso, B. Mennucci, and J. Tomasi, J. Chem. Phys. 122, 154501 (2005).
  18. B. Mennucci, Theor. Chem. Acc. (in press).
  19. G. Scalmani, M. Frisch, B. Mennucci, J. Tomasi, R. Cammi, and V. Barone, J. Chem. Phys.124, 094107 (2006).
  20. G. Scalmani, V. Barone, K. N. Kudin, C. S. Pomelli, G. E. Scuseria, and M. J. Frisch, Theor. Chem. Acc. 111, 90 (2004).
  21. This approximation is introduced here as it allows a more compact notation; we note, however, that in the computational code both formulations have been implemented and that numerical tests have shown an almost exact equivalence. We also remark that in the limit of an exact solution of the electrostatic problem, Eq. (8) is exactly fulfilled.
  22. F. Furche and R. Ahlrichs, J. Chem. Phys. 117, 7433 (2004).
  23. C. Van Caillie and R. D. Amos, Chem. Phys. Lett. 308, 249 (1999);
    24. 317, 159 (2000).
  24. N. C. Handy and H. F. Schaefer III, J. Chem. Phys. 81, 5031 (1984).
  25. M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN Development Version, Revision D.02, Gaussian, Inc., Wallingford, CT, 2004.
  26. C. J. F. Böttcher and P. Bordewijk, Theory of Electric Polarization (Elsevier, Amsterdam, 1978), Vol. 2.
  27. G. R. Fleming and M. Cho, Annu. Rev. Phys. Chem. 47, 109 (1996).
  28. For acroleina see, for example, F. Aquilante, V. Barone, and B. O. Roos, J. Phys. Chem. A 119, 12323 (2003);
    29. S. Andrade do Monte, T. Muller, M. Dallas, H. Lischka, M. Diedenhofen, and A. Klamt, Theor. Chem. Acc. 111, 78 (2004);
    whereas for MCP R. Cammi, L. Frediani, B. Mennucci, J. Tomasi, K. Ruud, and K. V. Mikkelsen, J. Chem. Phys. 117, 13 (2002);
    K. B. Wiberg and Y.-G. Wang, J. Phys. Chem. A 108, 9417 (2004).
  29. R. Jimenez, G. R. Fleming, P. V. Kumar, and M. Maroncelli, Nature (London) 369, 471 (1994).
  30. M. L. Horng, J. A. Gardecki, A. Papazyan, and M. Maroncelli, J. Phys. Chem. 99, 17311 (1995).
  31. B. M. Ladanyi and S. D. Schwartz, Theoretical Methods in Condensed Phase Chemistry (Kluwer, Dordrecht, The Netherlands, 2000).

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