Exploring time-dependent approaches towards the calculation of dynamics and spectroscopic signals: A mixed quantum/semiclassical wave packet method and the theory of transient absorption and femtosecond stimulated Raman scattering

Abstract

We present a time-dependent mixed quantum/semiclassical approach to calculating linear absorption spectra. Applying Variational Fixed Vibrational Basis/Gaussian Bath theory (FVB/GB) to the treatment of small molecules isolated in an extended cryogenic medium, an assumed time-scale separation between the few rapid, largely intramolecular modes of the guest and the several slower extended modes of the medium is utilized to partition a system from the surrounding bath. The system dynamics are handled with basis set methods, while the bath degrees of freedom are subject to a semiclasscial thawed Gaussian ansatz. The linear absorption spectrum for a realistic model system is calculated using FVB/GB results and then compared with a numerically exact calculation. Also contained in this dissertation are previously published theoretical works on Transient Absorption and Femtosecond Stimulated Raman Spectroscopy. Both encompass a rebuilding of the theory and elucidate the information content of the respective spectroscopic signals.

This dissertation includes previously published co-authored material.