Mixed quantum/classical (QM/CM) methods have often been utilized to theoretically study vibrational dynamics in condensed phase. Even if those methods can be relatively easily applied to study the dynamics of local environments around an uncoupled chromophore, it is still a computationally demanding job to directly apply those methods to many coupled chromophores, especially in the calculation of nonlinear response functions. In this case, the large dimensionality in two-exciton states often prohibites one from simple extension of the mixed QM/CM methods. Therefore we recently developed an approximate calculation method called time-averaging approximation in interaction picture to calculate absorption line shape of coupled chromophores and in this presentation, we will extend it to the calculation of the third-order nonlinear response function. As an example, we calculate 2DIR spectra of liquid water.

Time-averaging approximation to calculate nonlinear response function of coupled chromophores: Application to 2DIR spectroscopy of liquid water

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.