Journal of Chemical Physics, Vol.114, No.23, 10430-10435, 2001
Quadratic Brownian-oscillator model for solvation dynamics in optical response
The optical response of a chromophore coupled to a collective Gaussian solvation coordinate with a different curvature of the ground- and excited-state surfaces is studied. Exact:expressions are derived for the:time-dependent Stokes shift assuming an arbitrary solvent spectral density. Deviations from Onsager's linear fluctuation-dissipation relations between the Stokes shift and equilibrium fluctuations are discussed.