Photodynamics and ground state librational states of ClF molecule in solid Ar. Comparison of experiment and theory

Abstract

Photodynamics calculations of a ClF molecule in solid Ar are compared to experimental results and a new interpretation is given for the observed femtosecond-pump–probe signal modulation. We analyze the round-trip and depolarization times for the excited state wave-packet motion and discuss the incorporation of lattice cage motions that partially explain the time dependence of the measured signal. Librational eigenstates and eigenenergies are calculated by solving the rotational Schrödinger equation in the previously computed [T. Kiljunen, M. Bargheer, M. Gühr and N. Schwentner, Phys. Chem. Chem. Phys., 2004, 6, 2185–2197] octahedral potentials that hinder free molecular rotation in the solids. The obtained level structure is compared to infrared-spectroscopic results. We comment on the correspondence between temperature effects in the classical dynamics of the nuclei and the quantum mechanical probability distributions. We find the combinative treatment of different simulation temperatures congruous for interpreting the experimental results at cryogenic conditions.