Resonance Raman scattering from a multilevel, thermally relaxing system

Abstract

We consider light scattering from a multilevel system (e.g., a molecule) interacting with several heat baths. The Liouville space approach is employed and weak incident radiation intensity is assumed, whereas the light scattering process is described in the lowest appropriate order in the interaction between the molecule and the incident and emitted photons. The interaction with other radiation field modes as well as with the thermal baths is treated more fully, such as to account for the correct damping terms and their temperature dependence. The formalism is suited for light scattering from an impurity molecule in both gas and dense phases. The thermal baths induce relaxation within the manifold of excited states as well as transitions to nonradiative channels. Damping due to such transitions (as well as radiative damping) corresponds to interactions with zero temperature baths. The physical interpretation of such a bath depends on the nature of the particular damping process. Thermal relaxation within the excited manifold is induced by interaction with the environment represented by a bath of temperature T. Part of this interaction which is diagonal in the molecular space corresponds to the so‐called ’’quasielastic collisions’’ and induces modulations of the molecular energy levels and broadening of the relaxed emission. The remainder, nondiagonal part induces actual transitions between the excited molecular energy levels. The formalism yields in a single calculation expressions for the cross section for both the coherent (Raman) scattering process and the relaxed luminescence and enables us to discuss the effects of different factors such as temperature and quenching processes on the relative yields for these processes. The formalism also allows for interference between different levels of the excited manifold due to coupling of several levels to the same bath, and makes it possible to study the effect of thermal relaxation on these interference phenomena.