화학공학소재연구정보센터
Journal of Chemical Physics, Vol.110, No.20, 10067-10075, 1999
Smooth landscape solvent dynamics in electron transfer reactions
Solvent 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 gamma proportional to the contribution from the two parameters of the model. For the present model, gamma suggests the existence of "weak kinetic phase transitions," which are used in the analysis of solvent effects in charge-transfer reactions.