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Physical Review A

Theory of Collision Effects on Line Shapes Using a Quantum-Mechanical Description of the Atomic Center-of-Mass Motion — Application to Lasers. I

P. R. Berman, Willis E. Lamb

Published Dec 1, 1970• 72 citations
Publisher

Abstract

We present a theory of pressure effects in which the atomic center-of-mass motion is treated quantum mechanically. The quantum-mechanical calculation treats the perturber-induced energy-level variations and the velocity changes of the emitter caused by collisions on an equal basis. Specifically, we shall treat the problem of a laser to first order in the laser field, allowing for the fact that the laser atoms are undergoing collisions, but our results will also be applicable to the cases of stimulated emission or absorption. It will be sufficient to carry out a perturbation solution of the problem assuming that the laser atoms undergo at most one collision in their lifetime, since such a restricted calculation reveals the salient features of the theory. We shall find that, in general, there is no classical limit for our results. Thus, previous treatments employing a classical Boltzmann-equation approach for the atomic center-of-mass motion are invalid, and a quantum-mechanical description is necessary to correctly treat cases where both the modified Doppler effect (modified by collisions) and perturber-induced energy-level variations are present.

DOI
10.1103/physreva.2.2435

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We present a theory of pressure effects in which the atomic center-of-mass motion is treated quantum mechanically. The quantum-mechanical calculation treats the perturber-induced energy-level variations and the velocity changes of the emitter caused by collisions on an equal basis. Specifically, we shall treat the problem of a laser to first order in the laser field, allowing for the fact that the laser atoms are undergoing collisions, but our results will also be applicable to the cases of stimulated emission or absorption. It will be sufficient to carry out a perturbation solution of the problem assuming that the laser atoms undergo at most one collision in their lifetime, since such a restricted calculation reveals the salient features of the theory. We shall find that, in general, there is no classical limit for our results. Thus, previous treatments employing a classical Boltzmann-equation approach for the atomic center-of-mass motion are invalid, and a quantum-mechanical description is necessary to correctly treat cases where both the modified Doppler effect (modified by collisions) and perturber-induced energy-level variations are present.
The present paper includes the influence of collisions in the high-intensity laser theory by Stenholm and Lamb. The history of an atom is divided into field- and collision-dominated intervals. The collisions are treated as instantaneous independent events (impact approximation). The equation of motion for the density matrix of an ensemble of atoms undergoing collisions is derived. The collisions manifest themselves as an integral operator in the equation of motion. As a model, collisions which do not change the populations of the atomic levels are treated. Physical conditions on the kernel matrix of the collision integral are used to construct a simple nontrivial model. To simplify the treatment, the phase and velocity changes are assumed to take place in different collisions. This model is used to solve the problem of a high-intensity laser with collisions. Only the lowest nonvanishing terms in the Fourier expansion of the density matrix elements are used. Typical numerical results are evaluated and shown in the figures. Connections with other papers and generalizations are discussed.
Inelastic-collisional effects are incorporated into a quantum-mechanical transport equation (QMTE) that was developed in an earlier paper. The QMTE enables one to follow the quantum-state evolution of moving atoms which are interacting with some external fields while undergoing collisions with perturber atoms. The collisional processes are treated quantum mechanically and then reinterpreted in terms of classical variables so that the QMTE becomes an integrodifferential equation for atomic density-matrix elements containing both well-defined quantum-mechanical collision parameters (i.e., scattering amplitudes) and densitymatrix elements which are functions of classical position and velocity variables. Solutions of the QMTE enable one to derive line-shape formulas, and a discussion will be given of the general features to be expected for spectral profiles, Hanle-effect line shapes, and laser output curves, as well as the manner in which these features differ from those predicted by theories that neglect some quantum-mechanical aspects of the collision events. The inclusion of inelastic-collisional effects does not cover cases in which the frequency spacing of the atomic levels under consideration is comparable to the inverse duration time of a collision; nevertheless, the QMTE to be derived will be applicable to the analysis of a large number of atomic systems.
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.
An analytical description of long-range collisions between atoms in a laser cooling field is developed. We begin by considering an N-atom master equation. In the regime of low atomic densities (i.e., where the mean distance between two atoms is much larger than the laser wavelength) it is possible to treat the atom-atom interactions in perturbation theory. Furthermore we assume temperatures which allow a semiclassical treatment of the cooling process. The effect of the presence of other atoms can be separated analytically into two parts; an attenuation force due to the absorption of the laser beams in the atomic cloud similar to the results of Dalibard [Opt. Commun. 68, 203 (1988)], which tends to compress the atomic cloud, and a two-atom force due to photon emission and absorption cycles between different atoms. This force proves to be repulsive for the configurations studied and prevents the cloud from collapsing. The result for the first-order perturbation expansion in collision strength generalizes the model proposed by Walker, Sesko, and Wieman [J. Opt. Soc. B 8, 946 (1991)] by including additional terms, such as those associated with Raman couplings.
A theory of the influence of binary collisions on the line shapes associated with Doppler-free spectroscopy is presented. The specific calculation is for two-photon absorption through a real or virtual intermediate state, but the extension of the results to alternative level schemes is included. Collisions are treated quite generally at first, but, ultimately, a simple but reasonable collision model is adopted to properly account for both the "phase-interrupting" and "velocity-changing" aspects of collisions. It is shown that collisional processes can be used to distinguish between the "two-quantum" and "stepwise" contributions to the two-photon excitation rate. Moreover, it is demonstrated that systematic experimental line-shape investigations, in addition to providing tests of current collision theories, can lead to values for collision broadening and shift parameters, excitation transfer rates, magnetic substate relaxation rates, velocity-changing collision rates, and collision kernels. Consequently, Doppler-free spectroscopy can provide a new and important probe of collision effects in atomic and molecular systems.