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Physical Review A

Density-matrix correlations in the relaxation theory of electron broadening

Thomas Gomez, Taisuke Nagayama, David P. Kilcrease, Michael H Montgomery, Don E. Winget

Published Jul 16, 2018• 10 citations

Abstract

Spectral lines of radiating atoms are broadened by perturbations due to the surrounding plasma environment. In line-broadening calculations, the statistical average of the perturbation is weighted by the density matrix, which, in thermal equilibrium, contains correlations between the radiator and plasma. These correlations, however, have been neglected by all line-broadening theories except for the kinetic theory. The relaxation theory of line broadening is a mathematically exact derivation containing only one physical approximation: neglect of density-matrix correlations. We revisit this derivation and improve it by including the correlations. The line-broadening operator derived with the updated relaxation theory differs from that derived from the kinetic theory, though both derivations are considered to be exact. The kinetic theory derivation predicts that density-matrix correlations result a strong static shift of spectral lines. Our derivation, on the other hand, predicts that the correlations are a frequency-dependent effect that affects the line wings, and there is no shift of the line due to correlations. In addition, we predict that changes in the line shape due to correlations are only noticeable at extremely high densities. To distinguish the more appropriate model, we compare the shifts calculated with the relaxation and kinetic theory with data. The comparison shows support for the relaxation theory and casts into doubt the accuracy of the derivation of the kinetic theory of line broadening.

DOI: 10.1103/physreva.98.012505

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Spectral lines of radiating atoms are broadened by perturbations due to the surrounding plasma environment. In line-broadening calculations, the statistical average of the perturbation is weighted by the density matrix, which, in thermal equilibrium, contains correlations between the radiator and plasma. These correlations, however, have been neglected by all line-broadening theories except for the kinetic theory. The relaxation theory of line broadening is a mathematically exact derivation containing only one physical approximation: neglect of density-matrix correlations. We revisit this derivation and improve it by including the correlations. The line-broadening operator derived with the updated relaxation theory differs from that derived from the kinetic theory, though both derivations are considered to be exact. The kinetic theory derivation predicts that density-matrix correlations result a strong static shift of spectral lines. Our derivation, on the other hand, predicts that the correlations are a frequency-dependent effect that affects the line wings, and there is no shift of the line due to correlations. In addition, we predict that changes in the line shape due to correlations are only noticeable at extremely high densities. To distinguish the more appropriate model, we compare the shifts calculated with the relaxation and kinetic theory with data. The comparison shows support for the relaxation theory and casts into doubt the accuracy of the derivation of the kinetic theory of line broadening.

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.

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A complete stochastic theory of relaxation is developed in terms of a homogeneous equation for the averaged density matrix of a system immersed in a thermal bath.\nThis theory is then used as the basis of a new stochastic approach to the phenomenon of collisional broadening of spectral line shapes. Single photon and multiphoton processes are studied.\nThe features of a line shape are linked by simple expressions to the statistical properties of a stochastic hermitian Hamiltonian. The ordinary line shape predicted by Kubo's approach is generalized. The present approach predicts broadening as well as asymmetry and shift. A representation of line shapes in multiphoton processes by diagrams is also developed.

The shape of an isolated spectral transition is analyzed in terms of an approximation to the Waldmann–Snider kinetic equation. This equation is written in the form of a drift and collision operator acting on a density matrix. With the use of the spherical approximation, the collision operator is subdivided into an elastic Boltzmann-like collision term, an inelastic loss term, and a dephasing term. The Boltzmann-like term is responsible for Dicke narrowing of spectral lines, the inelastic loss term leads to line broadening and the dephasing term may contribute both to line broadening and shifting. Simple approximations to these terms are powerful enough to account for some of the details of experimental line shapes such as asymmetrical deviations from a Lorentzian line shape. Model numerical calculations are carried out assuming classical scattering potentials of the form 1/rn in the Boltzmann-like term and single complex frequencies for the other two. It was found that as long as the density was scaled to give the same diffusion constant, the exact form of the scattering cross section had little effect on the final line shape.