Speed-dependent Voigt dispersion line-shape function: applicable to techniques measuring dispersion signals

Abstract

An analytical expression for a Voigt dispersion line-shape function that incorporates speed-dependent effects (SDEs) on the collision broadening, applicable to spectroscopic techniques that measure dispersion signals, is presented. It is based upon a speed-dependent Voigt (SDV) model for absorption spectrometry that assumes that the molecular relaxation rate has a quadratic dependence on molecular speed. The expression is validated theoretically in the limit of small SDEs by demonstration that it reverts to the ordinary Voigt dispersion line-shape function and experimentally in a separate work by experiments performed by the noise-immune cavity-enhanced optical heterodyne molecular spectrometry technique. A comparison is given between the SDEs in the SDV absorption and dispersion line-shape functions. It is shown that both line shapes are affected significantly but differently by SDEs. The expression derived provides, for the first time to our knowledge, a possibility also for the techniques that measure dispersion signals to handle SDEs.