Product correlations in photofragment dynamics

Abstract

Correlations between either scalar or vector quantities measured in the study of photodissociation dynamics can serve to provide a very detailed picture of the dissociative event. This article discusses the use of Doppler profile and time-of-flight spectroscopy to learn about the correlation between the separate internal energies of two recoiling fragments, to study the way in which the internal energy distribution of a fragment varies with its recoil direction and to determine the angle between a photofragment's recoil velocity direction and its rotation vector. Two new techniques are introduced. High-voltage switching of the potential applied to a time-of-flight mass spectrometer is used to map the velocity distribution of photofragments onto their arrival time distribution. Probing of photofragments by polarized light with sub-Doppler resolution is used to determine the degree of angular correlation between their rotation vector and their recoil velocity vector.