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Journal of Physics B Atomic Molecular and Optical Physics

On the quantum stationary state method in line broadening theory

Henri Van Regemorter

Published Oct 14, 1992• 0 citations
Publisher

Abstract

The quantum stationary state method in the distorted wave Born approximation, applied to a two-body collision system in the presence of a radiation field, gives explicit expressions of the one-perturber profile and of the corresponding correlation function. The independent perturber approximation, when the two-body dynamic is separated from the statistical problem, is revisited without having recourse to a time-dependent formalism. Emphasis is given to broadening by electrons for which inelastic processes are important.

DOI
10.1088/0953-4075/25/19/009

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The quantum stationary state method in the distorted wave Born approximation, applied to a two-body collision system in the presence of a radiation field, gives explicit expressions of the one-perturber profile and of the corresponding correlation function. The independent perturber approximation, when the two-body dynamic is separated from the statistical problem, is revisited without having recourse to a time-dependent formalism. Emphasis is given to broadening by electrons for which inelastic processes are important.
Chapter 13 is devoted to two important approximation methods used to solve time-independent problems, namely stationary perturbation theory and the variational method. Perturbation theory is developed for both non-degenerate states and degenerate states, with illustrative examples. The Stark effect is considered separately. The dielectric constant of a transparent medium as a function of frequency is shown to result from the modification of the wave function due to the perturbation of the radiation field. Two complementary topics are presented: the canonical transformation method and the Feynman-Hellman method. Finally, the possibilities of the variational method are illustrated by using it first to determine an upper bound for the energy of the stationary states of a quantum system, and then to study more complicated cases, including the partially shielded Coulomb potential produced by a neutral atom.
Perturbation theory is applied to the interaction between a binary collisional system and a weak radiation field to obtain the rate of induced absorption or the line profile of an optically allowed transition at low density. The collisional system wave functions are not affected by the radiation field and appropriate different expansions of these functions must be used for the two electron-atom or atom-atom systems under study. Unified expressions of the profile are given which converges to the impact limit at small detunings. The semi-classical approach of the collisional problem is given to underline the correspondence with the usual autocorrelation formalism. Both approaches break down for large detunings where a quantum collisional theory must be used.
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 chapter, we present some fundamental issues about approximation methods that are often used when a quantum-mechanical system is perturbed and about the relationship between classical and quantum mechanics. In Sec. 10.1 we introduce the stationary perturbation theory, while Sec. 10.2 is devoted to time-dependent perturbations. In Sec. 10.3 we briefly examine the adiabatic theorem. In Sec. 10.4 we introduce the variation method, an approximation method that is not based on perturbation theory. In Sec. 10.5 we discuss the classical limit of the quantum-mechanical equations, whereas in Sec. 10.6 we deal with the semiclassical approximation, in particular the WKB method. On the basis of the previous approximation methods in Sec. 10.7 we present scattering theory. Finally, in Sec. 10.8 we treat a method that has a wide range of applications: the path-integral method. Stationary perturbation theory Perturbation theory is a rather general approximation method that may be applied when a small additional force (the perturbation) acts on a system (the unperturbed system), whose quantum dynamics is fully known. If the disturbance is small, it modifies both the energy levels and the stationary states. This allows us to make an expansion in power series of a perturbation parameter, which is assumed to be small. Perturbation theory may be applied both to the case where the additional force is time-independent (in which case a stationary treatment suffices – the subject of the present section) as well as to the case where it explicitly depends on time.
In all the applications of the formalism of quantum theory, we have considered mainly time-independent potential functions, V ( r , t ) = V ( r ). Such potentials made it easier to solve exactly the Schrodinger's equation or by solving the Schrodinger's equation approximately by using perturbation theory. The solution of the Schrodinger equation for time-independent potentials is obtained by using method of separable variables. The solution of time-independent Schrodinger gives stationary states, and the time dependence of the wave function is obtained by adding a phase factor to the stationary state. The schematic that follows describes such an approach ( Figure 7.1 ).
The line-shape function is expressed in terms of three boundary functions related to the two-particle Green's function. The transverse as well as the longitudinal interaction among atoms is considered, using the photon propagator approach. The broadening of one of the radiative states through the resonance interaction with the ground state is considered in detail. The contributions of multiple transfer of excitation and of two-body scattering are calculated separately. Several validity conditions are also obtained which clarify the approximations in the existing results. The velocity dependence of the width parameter is investigated in some detail; our results differ considerably from the existing results because we have included higher-order contributions. The extreme low-density region [where (collision width) \ensuremath{\sim} (natural width)] is also considered; the linewidth is found to be nonlinear in the number density. The additional contribution of the coupling between the radiative states is also calculated in a special case.