Laser-Induced Rate Processes in Gases: Dynamics, Unimolecular Decay, and Scattered Field

Abstract

We have recast a linear quantum-mechanical Boltzmann equation, describing the dynamics of a gas of $N$-level atoms absorbing light between an arbitrary pair of levels, into the form of a generalized master equation. The atoms are permitted to undergo both phase-changing and energy-changing collisions with a heat bath of inert molecules. The possibility of unimolecular decay is incorporated into the Boltzmann equation. The solutions of the generalized master equation give an accurate description of the system for short as well as long times and for arbitrary light-field intensity. Eigenvalues obtained from the solution of the $N$-level master equation are shown to have particular significance with regard to the scattered electromagnetic field, with the imaginary parts of the complex eigenvalues providing the location and the real parts of the eigenvalues giving the widths of scattered radiation bands. The dynamics and scattered field for a two-level system is discussed in detail. Two collision parameters giving the frequency of phase-changing and energy-changing collisions are important. For special values of these parameters, our results reduce to scattered field spectra calculated previously. When unimolecular decay is included, one identifies the smallest eigenvalue of the generalized master equation with the macroscopic rate constant. Observation of the scattered field for different incident field intensities would permit separation of radiative and thermal effects in an enhanced reaction rate, without requiring an accurate temperature measurement.