Nonlinear Spectroscopic Theory of Displaced Harmonic Oscillators with Differing Curvatures: A Correlation Function Approach

We present a theory for a bath model in which we approximate the adiabatic nuclear potential surfaces on the ground and excited electronic states by displaced harmonic oscillators that differ in curvature. Calculations of the linear and third-order optical response functions employ an effective short-time approximation coupled with the cumulant expansion. In general, all orders of correlation contribute to the optical response, indicating that the solvation process cannot be described as Gaussian within the model. Calculations of the linear absorption and fluorescence spectra resulting from the theory reveal a stronger temperature dependence of the Stokes shift along with a general asymmetry between absorption and fluorescence line shapes, resulting purely from the difference in the phonon side band. We discuss strategies for controlling spectral tuning and energy transfer dynamics through the manipulation of the excited-state and ground-state curvature. Calculations of the nonlinear response also provide insights into the dynamics of the system-bath interactions and reveal that multidimensional spectroscopies are sensitive to a difference in curvature between the ground- and excited-state adiabatic surfaces. This extension allows for the elucidation of short-time dynamics of dephasing that are accessible in nonlinear spectroscopic methods.