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Physical Review

A Note on Perturbation Theory as Applied to Collision Stimulated Processes

James N. Snyder, W. H. Furry

Published Aug 1, 1949• 1 citation
Publisher

Abstract

If a particle which can decay spontaneously is subjected to collisions with other particles the transition probability may be changed. The calculation of such an effect by the usual time-dependent perturbation methods is complicated by the circumstance that energy can be conserved in some intermediate states, because of the possibility of elastic scattering. The perturbation calculation is here modified in such a way that the resulting expression for the whole transition probability does not contain any divergences or spurious effects. By suitable approximations the expression is separated into two parts, one of which gives the probability of elastic scattering followed by a spontaneous transition, and the other the true stimulated transition probability which causes a change in the lifetime.

DOI
10.1103/physrev.76.359

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If a particle which can decay spontaneously is subjected to collisions with other particles the transition probability may be changed. The calculation of such an effect by the usual time-dependent perturbation methods is complicated by the circumstance that energy can be conserved in some intermediate states, because of the possibility of elastic scattering. The perturbation calculation is here modified in such a way that the resulting expression for the whole transition probability does not contain any divergences or spurious effects. By suitable approximations the expression is separated into two parts, one of which gives the probability of elastic scattering followed by a spontaneous transition, and the other the true stimulated transition probability which causes a change in the lifetime.
A systematic theory of sudden perturbations is derived for quantum systems whose states are described both by wave functions (a pure ensemble) and by a quantum density operator (a mixed ensemble). A perturbation series is written in powers of the parameter ωτ, which is small when the perturbation is sudden; ω is the typical eigenvalue of the unperturbed system; and τ is the characteristic collision time. When the perturbation (t), taken at different times, commutes with itself, the theory yields a compact analytic expression for the probabilities for stimulated transitions for any value of Vτ /. The results of many cross-section calculations for atomic collision processes are discussed from a common standpoint: the processes are treated as jarring processes which stimulate transitions in the quantum system. If a momentum δp is rapidly transferred to the system in a collision, regardless of the physical nature of the jarring, the probabilities for the stimulated transitions are governed by the parameter N ~δpδR/ where δR is a measure of the uncertainty in the coordinates which is due to the relatively slow motions in the unperturbed system.
We now consider systems for which the Hamiltonian contains time-dependent interaction terms. In such cases we cannot reduce the time-dependent Schro¨dinger equation to an eigenvalue equation. However, if the time-dependent terms can be regarded as small perturbations, we can develop a form of perturbation theory that can be used to calculate the effects of time-dependent terms. Consider a system for which the Hamiltonian may be written as the sum of a dominant unperturbed part Hˆ0 and a small perturbation Hˆ ′ as Hˆ = Hˆ0 + λHˆ ′(t) , (10.1.1) where the unperturbed Hamiltonian Hˆ0 is independent of time, whereas the perturbation Hˆ ′ may depend on time. The parameter 0 < λ < 1 has been introduced to keep track of various orders of approximations as in the case of time-independent perturbation theory discussed in Chapter 8. The basic idea is that a small perturbation to the Hamiltonian will produce a small change in the wave function. For a time-dependent perturbation, this change means that a system, initially in a particular eigenstate of Hˆ0, will find itself in a time-dependent admixture of the eigenstates. Thus the time-dependent perturbation causes the system to undergo transition to different eigenstates of Hˆ0. So for time-dependent perturbations our interest lies in calculating the probabilities for transition to different states.
This chapter examines applications drawn from perturbation theory. The main topic in perturbation theory is the energy and spontaneous decay rate of the 21-cm hyperfine line in atomic hydrogen. Before there were electronic computers, people had quite an accurate theoretical understanding of the energy levels in helium and more complicated systems. The trick was (and is) to find approximation schemes that treat unimportant parts of a physical system in quite crude approximations while reducing the interesting parts to a problem simple enough that it is feasible to compute but yet detailed enough to yield accurate results. The approximation methods in the chapter deal with the effects of small changes in the Hamiltonian, resulting for example from the application of a static or time variable electric or magnetic field. This may cause small changes in energy levels, and it may induce transitions among eigenstates of the original Hamiltonian.
Physically the examined perturbation problem can be regarded as a set of collision events of a time-independent perturbation potential with a quantum system. As an effect of collisions there is an expected definite change of energy of an initially unperturbed state of the system to some stationary perturbed state. The collision process certainly occupies some intervals of time which, however, do not enter the formalism. A striking property is the result of a choice of the sequence of collisions according to the applied circular scale of time: the scale produces almost automatically the energy terms predicted by the Schrödinger perturbation theory which usually is attained in virtue of complicated mathematical transformations. Beyond of the time scale and its rules—strictly connected with the perturbation order N introduced by Schrödinger—a partition process of the number N-1 is applied. This process, combined with contractions of the time points on the scale, provides us precisely with the perturbation terms entering the Schrödinger theory.
Perturbation theory for the interaction of light with a binary collisional system is applied to the calculation of line profiles, spontaneous emission rates and absorption or stimulated emission coefficients. For the usual radiation fields are perturber densities, this approximation is valid at all detunings Delta omega except the very narrow resonance region. Appropriate expansions of the total binary system wavefunctions give the emission and absorption profiles or rates, for atom-electron systems as well as for atom-atom systems, from the impact regime at small Delta omega up to the Born-Oppenheimer regime at very large Delta omega in collision-induced radiative transitions, the transitions being asymptotically allowed or forbidden. Emphasis is given to the proper averages and sums over initial and final states of the binary system which give rise to non-adiabatic effects. One shows that it is of crucial importance to include all dynamical effects during one collisional event before undertaking any calculation at small Delta omega where simultaneous collisions may occur.
The impulse approximation for the Rydberg atom-atom collisions is analyzed on the basis of the Faddeev equations. A modified expression is derived for the cross sections, including the interference between the Rydberg-electron--perturber scattering and the ion-core--perturber scattering. This expression is used for the calculations of the collisional quenching and elastic scattering in Rb(nS)-Rb and Rb(nP)-Rb collisions. We use the electron-Rb scattering phase shifts obtained from ab initio close-coupling calculations and their extrapolation, applying the modified effective-range theory. Our results show that the impulse approximation agrees with the experimental data for the quenching cross sections at n>20 but underestimates the quenching cross sections at lower n. The position of the maximum of the cross section is in good agreement with experimental data. We also obtain reasonable results for the elastic cross section at n>20, but for the lower n the results are too large. The interference effect plays a minor role in the process, which means that simultaneous electron-perturber and ion-perturber interaction is unlikely.