Theory of Pressure Broadening in an Adiabatic Representation

Abstract

The theory of pressure broadening by foreign atoms is formulated within the framework of an adiabatic representation (which we distinguish from the adiabatic approximation). This allows us to treat all the electrons in the gas as indistinguishable, and thus include the possibility of electron exchange between atoms; this effect, which is responsible for much of the interatomic interaction, is neglected in all previous theories, apart from the adiabatic and 'nearest neighbor' theories which are of limited applicability. By means of projection operators, we define a spectral matrix, whose dimension is equal to the number of distinct frequencies characteristic of the isolated radiator. The spectrum is equal to the sum of all the elements of the spectral matrix; the diagonal elements correspond to the different lines of the spectrum, and the off diagonal elements represent quantum interference between overlapping lines. The Fourier transform of the spectral matrix is the correlation matrix, whose elements time correlate components of the dipole moment operator responsible for different lines of the spectrum. The time evolution of the zero perturber correlation matrix is given by eiΩτ, where Ω is a diagonal matrix whose elements are the different frequencies characteristic of the radiator. The perturbing gas causes the 'reduced Liouvillian' Ω to acquire a time dependent or frequency dependent non-Hermitian nondiagonal part. To obtain low density approximations, we treat that non-Hermitian 'perturbation' to first order in the gas density.