Abstract
This chapter deals with several aspects of theory and computer simulation of solvation dynamics (SD), the solvent response to a change in solutesolvent interactions brought about by a solute electronic transition. The chapter starts with an overview of recent progress in SD research and with the basic assumptions that are used as a starting point in most SD theories and simulations. Instantaneous normal mode and time-domain methods of analysis of the solvation response applicable within the linear response approximation are then presented. Their use in uncovering several aspects of the molecular mechanism of SD, including the relative contributions of different molecular degrees of freedom, the collective nature of the response, the dependence of the response on the range and symmetry of the perturbation in solute-solvent interactions and the resemblance between SD and other experimentally-accessible solvent dynamics, is illustrated. It is shown how the results of this analysis can be used to develop approximations to SD in terms of single-solvent-molecule and pure solvent dynamics. Several causes of breakdown of the linear response approximation, relevant to SD in real systems, are discussed. Analysis of molecular dynamics simulation data on SD in benzene-acetonitrile mixtures is used to illustrate how to uncover the molecular mechanisms leading to nonlinear response and to show that significant nonlinearities can arise even for modest changes in the solute dipole.
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References
C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed. (VCH, New York, 1988).
M. Maroncelli, J. MacInnis, and G. R. Fleming, Science 243, 1674 (1989).
P. F. Barbara and W. Jarzeba, Adv. Photochem. 15, 1 (1990).
H. Heitele, Angew. Chem. 105, 378 (1993).
J. T. Hynes, in Ultrafast Dynamics in Chemical Systems, Vol. 7, edited by J. D. Simon (Kluwer, Dordrecht, 1994), pp. 345.
P. J. Rossky and J. D. Simon, Nature (London) 370, 263 (1994).
P. F. Barbara, T. J. Meyer, and M. A. Ratner, J. Phys. Chem. 100, 13148 (1996).
F. O. Raineri and H. L. Friedman, Adv. Chem. Phys. 107, 81 (1999).
J. T. Fourkas and M. Berg, J. Chem. Phys. 98, 7773 (1993).
J. T. Fourkas, A. Benigno, and M. Berg, J. Non-Cyst. Solids 172–174, 234 (1994).
P. Voehringer, D. C. Arnett, R. A. Westervelt, M. J. Feldstein, and N. F. Scherer, J. Chem. Phys. 102, 4027 (1995).
M. Berg, J. T. Fourkas, and A. Benigno, Proc. SPIE-Int. Soc. Opt. Eng. 2124, 88 (1994).
M. Berg, Chem. Phys. Lett. 228, 317 (1994).
M. D. Stephens, J. G. Saven, and J. L. Skinner, J. Chem. Phys. 106, 2129 (1997).
R. E. Larsen, E. F. David, G. Goodyear, and R. M. Stratt, J. Chem. Phys. 107, 524 (1997).
B. M. Ladanyi and R. M. Stratt, J. Phys. Chem. 100, 1266 (1996).
B. M. Ladanyi, in Electron Ion Transfer Condens. Media, edited by A. A. Kornyshev, M. Tosi, and J. Ulstrup (World Scientific, Singapore, 1997), pp. 110.
B. M. Ladanyi and R. M. Stratt, J. Phys. Chem. A 102, 1068 (1998).
B. M. Ladanyi and M. Maroncelli, J. Chem. Phys. 109, 3204 (1998).
G. Van der Zwan and J. T. Hynes, J. Phys. Chem. 89, 4181 (1985).
M. Maroncelli, V. P. Kumar, and A. Papazyan, J. Phys. Chem. 97, 13 (1993).
F. O. Raineri and H. L. Friedman, J. Chem. Phys. 101, 6111 (1994).
B. Bagchi, Annu. Rev. Phys. Chem. 40, 115 (1989).
A. Chandra, D. Wei, and G. N. Patey, J. Chem. Phys. 99, 4926 (1993).
P. G. Wolynes, J. Chem. Phys. 86, 5133 (1987).
I. Rips, J. Klafter, and J. Jortner, J. Phys. Chem. 94, 8557 (1990).
H. L. Friedman, B.-C. Perng, H. Resat, and F. O. Raineri, J. Phys.: Condens. Matter 6, A131 (1994).
F. O. Raineri, B.-C. Perng, and H. L. Friedman, Chem. Phys. 183, 187 (1994).
F. O. Raineri, H. Resat, B. C. Perng, F. Hirata, and H. L. Friedman, J. Chem. Phys. 100, 1477 (1994).
F. O. Raineri, H. L. Friedman, and B.-C. Perng, J. Mol. Liq. 73, 74, 419 (1997).
X. Song, D. Chandler, and R. A. Marcus, J. Phys. Chem. 100, 11954 (1996).
X. Song and D. Chandler, J. Chem. Phys. 108, 2594 (1998).
M. Maroncelli, P. V. Kumar, A. Papazyan, M. E. Horng, S. J. Rosenthal, and G. R. Fleming, in Ultrafast Reaction Dynamics and Solvent Effects, edited by Y. Gauduel and P. J. Rossky (American Institute of Physics, New York, 1994), pp. 310.
R. Jimenez, G. R. Fleming, P. V. Kumar, and M. Maroncelli, Nature (London) 369, 471 (1994).
R. S. Fee and M. Maroncelli, Chem. Phys. 183, 235 (1994).
D. Bingemann and N. P. Ernsting, J. Chem. Phys. 102, 2691 (1995).
M. Maroncelli and G. R. Fleming, J. Chem. Phys. 89, 5044 (1988).
J. S. Bader and D. Chandler, Chem. Phys. Lett. 157, 501 (1989).
R. M. Levy, D. B. Kitchen, J. T. Blair, and K. Krogh-Jespersen, J. Phys. Chem. 94, 4470 (1990).
T. Fonseca and B. M. Ladanyi, J. Phys. Chem. 95, 2116 (1991).
K. Ando and S. Kato, J. Chem. Phys. 95, 5966 (1991).
M. Maroncelli, J. Chem. Phys. 94, 2084 (1991).
E. A. Carter and J. T. Hynes, J. Chem. Phys. 94, 5961 (1991).
S. J. Rosenthal, R. Jimenez, G. R. Fleming, P. V. Kumar, and M. Maroncelli, J. Mol. Liq. 60, 25 (1994).
P. V. Kumar and M. Maroncelli, J. Chem. Phys. 103, 3038 (1995).
F. Cichos, R. Brown, U. Rempel, and C. Von Borczyskowski, J. Phys. Chem. A 103, 2506 (1999).
J. Lobaugh and P. J. Rossky, J. Phys. Chem. A 103, 9432 (1999).
P. F. Barbara, T. J. Kang, W. Jarzeba, and T. Fonseca, Jerusalem Symp. Quantum Chem. Biochem. 22, 273 (1990).
M. Maroncelli, J. Mol. Liq. 57, 1 (1993).
R. M. Stratt and M. Maroncelli, J. Phys. Chem. 100, 12981 (1996).
J. P. Hansen and I. R. McDonald, Theory of Simple Liquids, Second ed. (Academic Press, London, 1986).
D. K. Phelps, M. J. Weaver, and B. M. Ladanyi, Chem. Phys. 176, 575 (1993).
T. Fonseca and B. M. Ladanyi, J. Mol. Liq. 60, 1 (1994).
M. S. Skaf, I. A. Borin, and B. M. Ladanyi, Mol. Eng. 7, 457 (1997).
M. S. Skaf and B. M. Ladanyi, J. Phys. Chem. 100, 18258 (1996).
M. S. Skaf and B. M. Ladanyi, THEOCHEM 335, 181 (1995).
D. Laria and M. S. Skaf, J. Chem. Phys. 111, 300 (1999).
T. J. F. Day and G. N. Patey, J. Chem. Phys. 110, 10937 (1999).
A. A. Mosyak, O. V. Prezhdo, and P. J. Rossky, J. Chem. Phys. 109, 6390 (1998).
D. Aherne, V. Tran, and B. J. Schwartz, J. Phys. Chem. B 104, 5382 (2000).
B. M. Ladanyi and B.-C. Perng, manuscript in preparation (2000).
R. Richert, F. Stickel, R. S. Fee, and M. Maroncelli, Chem. Phys. Lett. 229, 302 (1994).
H. Wendt and R. Richert, Phys. Rev. E 61, 1722 (2000).
M. Lim, S. Gnanakaran, and R. M. Hochstrasser, J. Chem. Phys. 106, 3485 (1997).
B. D. Bursulaya, D. A. Zichi, and H. J. Kim, J. Phys. Chem. 100, 1392 (1996).
K. Ando, J. Chem. Phys. 107, 4585 (1997).
A. Chandra and B. Bagchi, J. Phys. Chem. 93, 6996 (1989).
D. Wei and G. N. Patey, J. Chem. Phys. 93, 1399 (1990).
U. Balucani and M. Zoppi, Dynamics of the liquid state (Oxford University Press, New York, 1994).
R. M. Stratt and M. Cho, J. Chem. Phys. 100, 5700 (1994).
B. M. Ladanyi and R. M. Stratt, J. Phys. Chem. 99, 2502 (1995).
B. M. Ladanyi and S. Klein, J. Chem. Phys. 105, 1552 (1996).
W. A. Steele, Mol. Phys. 61, 1031 (1987).
R. M. Stratt, Acc. Chem. Res. 28, 201 (1995).
T. Keyes, J. Phys. Chem. A 101, 2921 (1997).
J. E. Adams and R. M. Stratt, J. Chem. Phys. 93, 1332 (1990).
M. Buchner, B. M. Ladanyi, and R. M. Stratt, J. Chem. Phys. 97, 8522 (1992).
T. Keyes, J. Chem. Phys. 103, 9810 (1995).
M. Re and D. Laria, J. Phys. Chem. B 101, 10494 (1997).
M. Cho, S. J. Rosenthal, N. F. Scherer, L. D. Ziegler, and G. R. Fleming, J. Chem. Phys. 96, 5033 (1992).
E. W. Castner, Jr. and M. Maroncelli, J. Mol. Liq. 77, 1 (1998).
B. Bursulaya and H. J. Kim, J. Phys. Chem. B 101, 10994 (1997).
R. E. Larsen and R. M. Stratt, J. Chem. Phys. 110, 1036 (1999).
H. Stassen and W. A. Steele, J. Phys. Chem. B 101, 8774 (1997).
H. Stassen and W. A. Steele, J. Chem. Phys. 110, 7382 (1999).
M. Bruehl and J. T. Hynes, J. Phys. Chem. 96, 4068 (1992).
W. G. Rothschild, Dynamics of Molecular Liquids (Wiley, New York, 1984).
R. M. Lynden-Bell and W. A. Steele, J. Phys. Chem. 88, 6514 (1984).
H. L. Friedman, F. O. Raineri, B.-C. Perng, and M. D. Newton, J. Mol. Liq. 65/66, 7 (1995).
F. O. Raineri, B.-C. Perng, and H. L. Friedman, Electrochim. Acta 42, 2749 (1997).
D. M. F. Edwards, P. A. Madden, and I. R. McDonald, Mol. Phys. 51, 1141 (1984).
D. Bertolini and A. Tani, Mol. Phys. 75, 1065 (1992).
M. S. Skaf, T. Fonseca, and B. M. Ladanyi, J. Chem. Phys. 98, 8929 (1993).
B. M. Ladanyi and M. S. Skaf, J. Phys. Chem. 100, 1368 (1996).
M. S. Skaf, J. Chem. Phys. 107, 7996 (1997).
P. A. Bopp, A. A. Kornyshev, and G. Sutmann, J. Chem. Phys. 109, 1939 (1998).
B.-C. Perng and B. M. Ladanyi, J. Chem. Phys. 110, 6389 (1999).
L. Reynolds, J. A. Gardecki, S. J. V. Frankland, M. L. Horng, and M. Maroncelli, J. Phys. Chem. 100, 10337 (1996).
O. V. Prezhdo and P. J. Rossky, J. Phys. Chem. 100, 17094 (1996).
A. Mosyak, P. J. Rossky, and L. Turi, Chem. Phys. Lett. 282, 239 (1998).
B. M. Ladanyi and B.-C. Perng, work in progress (2000).
R. Olender and A. Nitzan, J. Chem. Phys. 102, 7180 (1995).
J. Faeder and B. M. Ladanyi, Manuscript in preparation (2000).
D. Pant, R. E. Riter, and N. E. Levinger, J. Chem. Phys. 109, 9995 (1998).
D. M. Willard, R. E. Riter, and N. E. Levinger, J. Am. Chem. Soc. 120, 4151 (1998).
R. E. Riter, D. M. Willard, and N. E. Levinger, J. Phys. Chem. B 102, 2705 (1998).
J. Faeder and B. M. Ladanyi, J. Phys. Chem. B 104, 1033 (2000).
S. A. Kovalenko, J. Ruthmann, and N. P. Ernsting, J. Chem. Phys. 109, 1894 (1998).
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Ladanyi, B.M. (2002). Mechanistic Studies of Solvation Dynamics in Liquids. In: Schwartz, S.D. (eds) Theoretical Methods in Condensed Phase Chemistry. Progress in Theoretical Chemistry and Physics, vol 5. Springer, Dordrecht. https://doi.org/10.1007/0-306-46949-9_7
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DOI: https://doi.org/10.1007/0-306-46949-9_7
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