Stimulated Raman signals at conical intersections: Ab initio surface hopping simulation protocol with direct propagation of the nuclear wave function

Markus Kowalewski; Shaul Mukamel

doi:10.1063/1.4927475

Stimulated Raman signals at conical intersections: Ab initio surface hopping simulation protocol with direct propagation of the nuclear wave function

J Chem Phys. 2015 Jul 28;143(4):044117. doi: 10.1063/1.4927475.

Authors

Markus Kowalewski¹, Shaul Mukamel¹

Affiliation

¹ Department of Chemistry, University of California, Irvine, California 92697-2025, USA.

PMID: 26233117
DOI: 10.1063/1.4927475

Abstract

Femtosecond Stimulated Raman Spectroscopy (FSRS) signals that monitor the excited state conical intersections dynamics of acrolein are simulated. An effective time dependent Hamiltonian for two C-H vibrational marker bands is constructed on the fly using a local mode expansion combined with a semi-classical surface hopping simulation protocol. The signals are obtained by a direct forward and backward propagation of the vibrational wave function on a numerical grid. Earlier work is extended to fully incorporate the anharmonicities and intermode couplings.