Effects of finite laser pulse width on two-dimensional electronic spectroscopy

Abstract

We combine the hierarchical equations of motion method and the equation-of-motion phase-matching approach to calculate two-dimensional electronic spectra of model systems. When the laser pulse is short enough, the current method reproduces the results based on third-order response function calculations in the impulsive limit. Finite laser pulse width is found to affect both the peak positions and shapes, as well as the time evolution of diagonal and cross peaks. Simulations of the two-color two-dimensional electronic spectra also show that, to observe quantum beats in the diagonal and cross peaks, it is necessary to excite the related excitonic states simultaneously.