Two valence bond state model for molecular nonlinear optical properties. Nonequilibrium solvation formulation

Journal of Physical Chemistry A

Volumn 102, Issue 39, 1998, Pages 7712-7722

  Thompson, Ward H ^a   Blanchard Desce, Mireille ^b   Hynes, James T ^a  

^a UNIVERSITY OF COLORADO   (United States)

^b ECOLE NORMALE SUPÉRIEURE   (France)

Author keywords

[No Author keywords available]

Indexed keywords

CALCULATIONS; ELECTRONIC STRUCTURE; FREE ENERGY; GROUND STATE; MATHEMATICAL MODELS; OPTICAL PROPERTIES; SOLVENTS; SURFACES;

BOND LENGTH ALTERNATION; DIABATIC GAP; HYPER POLARIZABILITY; NONEQUILIBRIUM SOLVATION; POLYENE; SOLVENT POLARITY; TWO VALENCE BOND STATE MODEL;

MOLECULES;

EID: 0032164495     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp981916j     Document Type: Article

References (78)

1. Oudar, J. L.; Chemla. D. S. J. Chem. Phys. 1977, 66, 2664. Oudar, J. L. J. Chem. Phys. 1977, 67, 446.
2. Oudar, J. L.; Chemla. D. S. J. Chem. Phys. 1977, 66, 2664. Oudar, J. L. J. Chem. Phys. 1977, 67, 446.
3. Chemla, D. S.; Zyss, J., Eds. Nonlinear Optical Properties of Organic Molecules and Crystals; Academic Press. Inc.; New York, 1987.
4. Marder, S. R.; Perry, J. W.; Bourhill. G.; Gorman, C. B.; Tiemann, B. G.; Mansour, K. Science 1993, 261, 186.
5. Gorman, C. B.; Marder, S. R. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 11297.
6. Marder, S. R.; Gorman, C. B.; Meyers, F.; Perry, J. W.; Bourhill, G.; Brédas, J.-L.; Pierce, B. M. Science 1994, 261, 632.
7. Gorman, C. B.; Marder, S. R. Chem. Mater. 1995, 7, 215.
8. Lu, D.; Chen, G.; Perry, J. W.; Goddard, W. A., III. J. Am. Chem. Soc. 1994, 116, 10679.
9. Chen, G.; Lu, D.; Goddard, W. A., III. J. Chem. Phys. 1994, 101, 5860.
10. See also Castiglioni, C; Del Zoppo, M.; Zerbi, G. Phys. Rev. B 1996, 53, 13319.
11. Barzoukas, M.; Runser, C.; Fort, A.; Blanchard-Desce, M. Chem. Phys. Lett. 1996, 257, 531.
12. Barzoukas, M.; Fort, A.; Blanchard-Desce, M. J. Nonlin. Opt. Phys. Mater. 1996, 5, 757.
13. Barzoukas, M.; Fort, A.; Blanchard-Desce, M. New J. Chem. 1997, 21, 309. Blanchard-Desce, M.; Barzoukas, M. J. Opt. Soc. Am. B 1998, 15, 302.
14. Barzoukas, M.; Fort, A.; Blanchard-Desce, M. New J. Chem. 1997, 21, 309. Blanchard-Desce, M.; Barzoukas, M. J. Opt. Soc. Am. B 1998, 15, 302.
15. Fort, A.; Barzoukas, M.; Muller, J.; Alain, V.; Blanchard-Desce, M. J. Lumin. 1997, 72-74, 494.
16. Perry, J. W.; Marder, S. R.; Meyers, F.; Lu, D.; Chen, G.; Goddard, W. A., III; Brédas, J.-L.; Pierce, B. M. In Polymers for Second-Order Nonlinear Optics: Lindsay, G. A., Singer, K. D., Eds.; ACS Symposium Series 601; American Chemical Society: Washington, DC, 1995; p 45.
17. Stähelin, M.; Burland, D. M.; Rice, J. E. Chem. Phys. Lett. 1992, 191, 245.
18. Yu, J.; Zerner, M. C. J. Chem. Phys. 1994, 100, 7487.
19. Di Bella, S.; Marks, T. J.; Ratner, M. A. J. Am. Chem. Soc. 1994, 116, 4440.
20. Albert, I. D. L.; Marks, T. J.; Rainer, M. A. J. Phys. Chem. 1996, 100, 9714.
21. Gao, J.; Alhambra, C. J. Am. Chem. Soc. 1991, 119, 2962.
22. Willetts, A.; Rice, J. E. J. Chem. Phys. 1993, 99, 426.
23. Mikkelsen, K. V.; Luo, Y.; Agren, H.; Jorgensen, P. J. Chem. Phys. 1994, 100, 8240.
24. Mikkelsen, K. V.; Sylvester-Hvid, K. O. J. Phys. Chem. 1996, 100, 9116.
25. Cammi, R.; Cossi, M.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1996, 105, 10556.
26. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
27. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
28. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
29. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
30. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
31. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
32. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437. Marcus, R. A.; Sutin, N. Biochim. Biophvs. Acta 1985, 811, 265. Brown, D. B., Ed. Mixed-Valence Compounds; Reidel: Dordrecht, 1980. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115. Bagchi, B.; Chandra, A. Adv. Chem. Phys. 1991, 80, 1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
33. Marcus, R. A. J. Chem. Phys. 1956, 24, 966.
34. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
35. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
36. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
37. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
38. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
39. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
40. Mathis, J. R.; Kim, H. J.; Hynes, J. T. J. Am. Chem. Soc. 1993, 115, 8248. Peslherbe, G. H.; Bianco, R.; Ladanyi, B. M.; Hynes, J. T. J. Chem. Soc. Faraday Trans. 1997, 93, 977. Gertner, B. J.; Ando, K.; Bianco, R.; Hynes, J. T. Chem. Phys. 1994, 183, 309. Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431. See also: Kim, H. J.; Hynes, J. T. J. Photochem. Photobiol. A 1997, 105, 337. Sumi, H.; Marcus. R. A. J. Chem. Phys. 1986, 84, 4272. Kim, H. J. J. Chem. Phys. 1997, 106, 5979.
41. Barbara, P. F.; Jarzeba, W. Adv. Photochem. 1990, 15, 1. Maroncelli, M. J. Mol. Liq. 1993, 57, 1.
42. Barbara, P. F.; Jarzeba, W. Adv. Photochem. 1990, 15, 1. Maroncelli, M. J. Mol. Liq. 1993, 57, 1.
43. 7.8 (though this could be related to delocalized character of the charges within the donor and acceptor groups).
44. Pauling, L. Proc. Nat. Acad. Sci. 1939, 25, 577.
45. Murrell, J. N. The Theory of the Electronic Spectra of Organic Molecules; Wiley: New York, 1963.
46. Since nuclear positions do not change in Franck-Condon transitions, entropies remain unchanged so that free energy differences are the same as energy differences.
47. Zichi, D. A.; Ciccotti, G.; Hynes, J. T.; Kapral, R. J. Phys. Chem. 1989, 93, 6261.
48. This is an oversimplification; see ref 18 and the discussion around eq 2.20.
49. The two-level expression of (hyper)polarizabilities are easily derived using the quantum-perturbed expressions given in: Ward, J. F. Rev. Mod. Phys. 1965. 37, 1.
50. eg.
51. 34 in terms of a molecule in a constant external electric field of infinite wavelength, such that the dipole moment can be used to characterize the molecule. On the other hand, a point dipole description of the solute molecule in interaction with polarization fields in the solvent is not expected to be very accurate for solutes the size of the push-pull polyenes and is avoided in the present treatment.
52. Willetts, A.; Rice, J. E.; Burland, D. M.; Shelton, D. P. J. Chem. Phys. 1992, 97, 7590.
53. 0 holds that the two conditions coincide. Note also that when the mirror condition holds MIX becomes proportional to BLA. See also ref 18 for a related discussion.
54. It was assumed in ref 8 that the neutral state carries no dipole moment, but this is a detail irrelevant for the main point made in the text.
55. eq = -1: an equilibrium solvation based relation such as eq 2.26 will predict no solvent effect, whereas the nonequilibrium solvation based eq 2.25 predicts a solvent influence on the diabatic gap (see also Figure 1).
56. 11
57. Blanchard-Desce, M.; Alain, V.; Midrier, L.; Wortmann, R.; Lebus, S.; Glania, C.; Krämer, P.; Fort, A.; Muller, J.; Barzoukas, M. J. Photochem. Photobiol. A 1997, 105, 115.
58. F, is always the same, independent of what the composition of the ground adiabatic state might be: in a Franck-Condon transition between two VB states, the solvent electronic polarization adjusts instantly.
59. e.g can be developed.
60. Weast, R. C., Ed. CRC Handbook of Chemistry and Physics; CRC Press. Inc..;Boca Raton, FL, 1983.
61. 45 unfortunately, for most of the molecules solubility requirements for the various polarizability measurements rule this out.
62. s = t to a very good approximation.
63. max: 546 (cyclohexane); 556 (dioxane); 556 (diethyl oxide); 569 (ethyl acetate); 572 (tetrahydrofurane); 584 (dichloromethane); 578 (acetone); 581 (acetonitrile); 591 (DMF); 598 (DMSO).
64. N = 17.3 D from Table I, this gives ΔQ = 0.40e. (See also ref 28.)
65. Muller, J.; Fort. A.; Barzoukas, M.; Alain, V.; Blanchard-Desce, M. Work in progress.
66. As noted in refs 44, 47, 52, and 57, refinements can be made within the basic two VB state description presented herein.
67. eq, and t are extracted from experiment in low-polarity solvents, and that the practice in the present work of referencing quantities to the low-polarity case includes them as well.
68. Klamt, A. J. Phys. Chem. 1996, 100, 3349.
69. As an illustration for an environment somewhat more complex than simple solutions, one could consider the environment of an electrolyte solution (van der Zwan. G.; Hynes, J. T. Chem. Phys. 1991 152, 169). in which dissolved ions contribute to the "solvation" ingredients.
70. Marder. S. R.; Kippelen, B.; Jen, A. K.-Y.; Peyghambarian. Nature 1997, 28, 845.
71. Kim, H. J.; Hynes, J. T. J. Chem. Phys. 1992, 96, 5088.
72. el is the characteristic frequency of the solvent electronic polarization, which can be approximated by the solvent electronic absorption energy. The Born-Oppenheimer limit for the solvent electronic polarization is given by ρ → 0. For the molecules and solvents considered here ρ < 2/3. See Appendix C of ref 56 for the relevant equations.
73. Lu, D.; Chen, G.; Goddard, W. A.. III. J. Chem. Phys. 1994, 101, 4920.
74. Bianco, R.; Juanos i Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1994, 98, 12103. Bianco, R.; Hynes, J. T. J. Chem. Phys. 1995, 102, 7864, 7885.
75. Bianco, R.; Juanos i Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1994, 98, 12103. Bianco, R.; Hynes, J. T. J. Chem. Phys. 1995, 102, 7864, 7885.
76. This assumes that vibrational relaxation is rapid compared to solvation dynamics proper, which is not guaranteed. In addition, the excited-state charge distribution will evolve from that reached in the Franck-Condon transition to that appropriate to equilibrium; such a feature is not included in standard descriptions, which assume, e.g., a fixed dipole moment in the excited state. This feature is incorporated in the present description.
77. Such experiments could also indicate if other geometrical coordinates (e.g. cis-trans isomerization) are necessary beyond the BLA coordinate.
78. Plaza, P.; Martin, M.; Laage, D.; Barbosa, E.; Alain, V.; Blanchard-Desce, M. Work in progress.