Effects of collisions on linear and non-linear spectroscopic line shapes

A fundamental physical problem is the determination of atom-atom, atom-molecule and molecule-molecule differential and total scattering cross sections. In this work, a technique for studying atomic and molecular collisions using spectroscopic line shape analysis is discussed. Collisions occuring within an atomic or molecular sample influence the sample's absorptive or emissive properties. Consequently the line shapes associated with the linear or non-linear absorption of external fields by an atomic system reflect the collisional processes occuring in the gas. Explicit line shape expressions are derived characterizing linear or saturated absorption by two- or three-level “active” atoms which are undergoing collisions with perturber atoms. The line shapes may be broadened, shifted, narrowed, or distorted as a result of collisions which may be “phase-interrupting” or “velocity-changing” in nature. Systematic line shape studies can be used to obtain information on both the differential and total active atom-perturber scattering cross sections.