Leite, Vitor Barbanti Pereira [UNESP]2014-05-272014-05-271999-05-22Journal of Chemical Physics, v. 110, n. 20, p. 10067-10075, 1999.0021-9606http://hdl.handle.net/11449/65778Solvent effects play a major role in controlling electron-transfer reactions. The solvent dynamics happens on a very high-dimensional surface, and this complex landscape is populated by a large number of minima. A critical problem is to understand the conditions under which the solvent dynamics can be represented by a single collective reaction coordinate. When this unidimensional representation is valid, one recovers the successful Marcus theory. In this study the approach used in a previous work [V. B. P. Leite and J. N. Onuchic; J. Phys. Chem. 100, 7680 (1996)] is extended to treat a more realistic solvent model, which includes energy correlation. The dynamics takes place in a smooth and well behaved landscape. The single shell of solvent molecules around a cavity is described by a two-dimensional system with periodic boundary conditions with nearest neighbor interaction. It is shown how the polarization-dependent effects can be inferred. The existence of phase transitions depends on a factor y proportional to the contribution from the two parameters of the model. For the present model, γ suggests the existence of weak kinetic phase transitions, which are used in the analysis of solvent effects in charge-transfer reactions. © 1999 American Institute of Physics.10067-10075engArtigo10.1063/1.478880WOS:000080367700032Acesso restrito2-s2.0-00056356782-s2.0-0005635678.pdf0500034174785796