Comprehensive theory for line broadening in high-resolution and nonlinear spectroscopies: application to the Na D lines

Abstract

A general method for analysing line broadening caused by Doppler, phaseshift, inelastic and velocity-changing collisional effects is proposed for transitions at optical wavelengths. In a unified approach Poisson statistics are used to describe collision probabilities randomly distributed in a time interval which can terminate the optical coherence in a combination of the above effects; markoffian independence is assumed for each collision. Then the dipole moment correlation function is obtained in a form which is virtually exact in accounting for all effects of isotropic forces, and which is correct to second-order terms in the anisotropic interaction potentials. Phenomena as diverse as standard optical pressure broadening, broadening due to velocity-changing collisions in nonlinear spectroscopies, and Dicke narrowing of the Doppler contour are described. The implications of the theory are discussed in detail and applied to the case of the NaD lines perturbed by He buffer gas. Numerical calculations reveal that the substantially different lineshift and broadening parameters in nonlinear and in standard optical spectroscopies can be reasonably well understood within the limitations posed by present uncertainties in the Na 32P-He interaction potentials. However, the large differences in shift and width between the D2 and D1 lines in saturation spectroscopy cannot be explained within the present theory.