Solving the line-shape problem with speed-dependent broadening and shifting and with Dicke narrowing. I. Formalism

Abstract

In this paper, we present a formalism for the exact calculation of spectral profile of an isolated line undergoing speed-dependent collisional broadening and shifting and Dicke narrowing. It is couched in the language of the density matrix as in the closely related fields of transport phenomena, laser physics, and nonlinear optics. The formalism is ab intio in spirit, permitting the calculation of the line shape starting only from a given interaction potential. The line shape is obtained by solving a transport/relaxation equation for the off-diagonal element of the density matrix, a macroscopic quantity. The collision operator in the transport/relaxation equation, which is determined from the (microscopic) interaction between the active molecule and the perturber, is presumed known.