We investigate an alternative approach to the study of the solvent response
to the sudden change in the charge distribution of a solute molecule. The
theory avoids the assumption that the response induced in the solvent is li
near with respect to the solute perturbation. Our method focuses on the non
equilibrium characteristic function g(u)(alpha;t) for the solvent contribut
ion to the vertical energy gap, which provides a link between the averages
measured in the solvation dynamics experiment and the molecular description
of the nonequilibrium solvation process. We take advantage of the Kawasaki
form of the nonequilibrium distribution function, which is valid only in t
he case of jump perturbations, to express the characteristic function as a
ratio of two partition functions defined in terms of complex-valued, time-d
ependent, many-body effective Hamiltonians. We then apply the theory of the
generalized Langevin equation to cast the partition functions in terms of
approximate two-body additive effective Hamiltonians, in a way that enables
us to exploit well known nonlinear equilibrium integral equation methodolo
gies to investigate the process of nonequilibrium solvation on a molecular
scale. To test the performance of our simplest approximation fur g(u)(alpha
: t) we report calculations of the nonequilibrium solvation rime correlatio
n function and of the evolution of the solvation structure for a model syst
em (first studied by Fonseca and Ladanyi by molecular dynamics computer sim
ulations) that displays important nonlinear effects.