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The Journal of Chemical Physics

A modified Boltzmann kinetic equation for line shape functions

Robert Blackmore

Published Jul 15, 1987• 52 citations
Publisher

Abstract

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.

DOI
10.1063/1.453286

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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.
In this paper, we present a formalism for the exact calculation of spectral profile of an isolated line undergoing speed-dependent collisional broadening and shifting and Dicke narrowing. It is couched in the language of the density matrix as in the closely related fields of transport phenomena, laser physics, and nonlinear optics. The formalism is ab intio in spirit, permitting the calculation of the line shape starting only from a given interaction potential. The line shape is obtained by solving a transport/relaxation equation for the off-diagonal element of the density matrix, a macroscopic quantity. The collision operator in the transport/relaxation equation, which is determined from the (microscopic) interaction between the active molecule and the perturber, is presumed known.
A new approach is suggested for dealing with the many-body aspects of resonance broadening of spectral lines in gases. A Liouville-space formalism is used in which the absorption by NNN identical molecules undergoing resonance-exchange collisions is described by an NNN-dimensional projection operator in Liouville space. In the impact approximation, under conditions in which the Doppler shift of resonance frequencies can be neglected, it is shown that the effect of resonance collisions is to modify the linewidth expression obtained by ordinary foreign-gas-type theories. The shape of isolated lines remains, however, Lorentzian. Only a combined effect of Doppler and collision broadening causes appreciable deviations from the Lorentzian shape near the line center, but these deviations are not peculiar to resonance broadening.
The thermally averaged collision-broadened line shape is written in terms of a detuning-dependent broadening rate ${\ensuremath{\gamma}}_{c}(\ensuremath{\Delta})$ which is evaluated numerically for van der Waals potentials using classical straight trajectories. The results are presented in terms of reduced variables that make it easy to calculate the line shape for any system with arbitrary van der Waals coefficient and temperature. The results show how the line shape makes a smooth transition from a Lorentzian profile in the impact region to the dramatically asymmetric far line wings. The transition zone is characterized by $|\ensuremath{\Delta}|{T}_{d}\ensuremath{\sim}1$, where $\ensuremath{\Delta}$ is the frequency detuning from resonance and Td{T}_{d}Td​ is a characteristic collision duration. The lowest-order correction to the Lorentzian line shape due to finite collision duration describes the dominant behavior for $|\ensuremath{\Delta}|{T}_{d}\ensuremath{\sim}1$. The numerical results are compared with analytic approximations and recent experiments. Averaging over a thermal distribution of relative velocities is shown to alter the line-shape asymmetry substantially, improving agreement between theory and experiment. The temperature dependence of the overall line shape is presented and discussed.
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 3 2 P-He interaction potentials. However, the large differences in shift and width between the D 2 and D 1 lines in saturation spectroscopy cannot be explained within the present theory.
The work of two previous papers is extended and a theory of pressure broadening is developed which treats the perturbers quantum mechanically and allows for inelastic collisions, degeneracy, and overlapping lines. The impact approximation is used. It consists in assuming that it takes, on the average, many collisions to produce an appreciable disturbance in the wave function of the atom, and it results in an isolated line having a Lorentz shape. Validity criteria are given. When the approximation is valid, it is allowable to replace the exact, fluctuating interaction of the perturbers with the atom by a constant effective interaction. The effective interaction is expressed in terms of the one-perturber quantum mechanical transition amplitudes on and near the energy shell and its close relationship to the scattering matrix is stressed. The calculation of the line shape in terms of the effective interaction is the same as when the perturbers move on classical paths. Results are written explicitly for isolated lines. If the interaction of the perturbers with the final state can be neglected, the shift and width are proportional to the real and imaginary part of the forward elastic scattering amplitude, respectively. By the optical theorem, the width can also be written in terms of the total cross section. When the interaction in the final state cannot be neglected, the shift and width are still given in terms of the elastic scattering amplitudes, in a slightly more complicated fashion. Finally, rules are given for taking into account rotational degeneracy of the radiating states.
In this paper general expressions for the width and shift of atomic lines produced by fast electron collisions are obtained. We use the recent quantum-mechanical theories developed to explain the pressure line shape in the impact approximation. Only isolated and Lorentzian lines are analyzed. The calculations are performed by expanding the scattering matrix up to the second Born approximation. The contributions of both elastic and inelastic virtual collisions are calculated. Degenerate and nondegenerate atomic states are considered.