Simulations of Solvation Dynamics Using a Nonlinear Response Approach

Simulations of the time evolution of the probability distribution function of the solvation coordinate of a solute in liquid solution are presented. Assuming impulsive excitation of the ground-state population to the excited-state free energy surface, the time dependence of the probability distribution function of the solvation coordinate is obtained by solving the Smoluchowski diffusion equation. Emphasis is on the influence of anharmonicity in the expression for the free energy surfaces on the solvation dynamics and its implications for time-resolved fluorescence measurements.