화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.119, No.34, 11063-11067, 2015
Projection of the Dynamics of Electron Transfer Reaction in Dual Space onto the One-Dimensional Slower Reaction Coordinate Axis
We have derived here for the first time an exact dynamical equation within the domain of classical mechanics for the time dependent density distribution function of one-dimensional reaction coordinate (RC) in the condensed phase for electron transfer reaction by projecting the dynamics of slower modes in multidimensional Liouville space starting with a given set of coordinates of the faster modes. After the faster modes were ensemble averaged, the dynamics of the whole system solely depends on the slower RC. To simplify the complicated equation into a tractable form, benchmark approximations are employed to reduce the formally exact equation into an equation similar to the Smoluchowski equation with a delocalized sink term. As a test case, a Hamiltonian for the solute solvent system modeled by quadratic functions for fast-relaxing vibrational and slow-relaxing polarization modes, respectively, has been considered. Interestingly, our simplified model Hamiltonian is transformed into the well-known phenomenological Sumi Marcus kinetic equation corresponding to this equation.