Vibrational State Analysis of Electronic-To-Vibrational Energy Transfer Processes

Abstract

The quenching of electronic fluorescence has been studied extensively in a wide variety of atomic and molecular systems over the past several years (1). Nevertheless, most of these quenching experiments have given little information concerning the specific product states into which electronic energy is channeled during collision, the relative amount of electronic energy converted to translational, rotational , and vibra­ tional energy, or the specific rate constants for energy transfer into a given channel. Comprehensive studies of vibration-vibration (V-V) and vibration-translation/ rotation (V-T/R) energy transfer phenomena have been made for many molecules over the past few years (2). These studies have provided a rather detailed view of such processes in the ground electronic states of molecules. Partly due to the develop­ ment of lasers and new experimental techniques and partly due to the increased knowledge of energy transfer processes, there has been renewed interest in the study of electronic-to-vibrational (E-V) energy transfer, which can provide insight into molecular interactions and energy partitioning during collisions. Such studies are of fundamental interest as tests of necessarily approximate scattering theories and as probes of potential surface crossings that play important roles in chemically