A comparison between different semiclassical approximations for optical response functions in nonpolar liquid solutions

The temporal behavior of optical response functions (ORFs) reflects the quantum dynamics of an electronic superposition state, and as such lacks a well-defined classical limit. In this paper, we consider the importance of accounting for the quantum nature of the dynamics when calculating ORFs of different types. To this end, we calculated the ORFs associated with the linear absorption spectrum and the nonlinear two-pulse photon-echo experiment, via the following approaches: (1) the semiclassical forward-backward approach; (2) an approach based on linearizing the path-integral forward-backward action in terms of the difference between the forward and backward paths; (3) an approach based on ground state nuclear dynamics. The calculations were performed on a model that consists of a two-state chromophore solvated in a nonpolar liquid. The different methods were found to yield very similar results for the absorption spectrum and “diagonal” two-pulse photon echo (i.e., the homodyne-detected signal at time $t=t0$ after the second pulse, where $t0$ is the time interval between the two pulses). The different approximations yielded somewhat different results in the case of the time-integrated photon-echo signal. The reasons for the similarity between the predictions of different approximations are also discussed