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Physical Review

New Formulation of Time-Dependent Perturbation Theory

Kwong T. Chung

Published Nov 25, 1967• 29 citations
Publisher

Abstract

The previous time-dependent variation-perturbation theory, which is derived from the conventional time-dependent perturbation equations, contains two inconvenient features. When the perturbation becomes static, the wave function so obtained does not satisfy the time-dependent Schr\"odinger equation, and the perturbation equations cannot be reduced to the ordinary time-independent perturbation equations. To remove these difficulties, we introduce a perturbed time-dependent phase factor in deriving a new set of perturbation equations. We then construct the variation-perturbation functionals as in the previous theory; the perturbed wave functions are solved by minimizing these functionals. The same method is also applied to many-electron systems, using the coupled and uncoupled Hartree-Fock scheme.

DOI
10.1103/physrev.163.1343

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The previous time-dependent variation-perturbation theory, which is derived from the conventional time-dependent perturbation equations, contains two inconvenient features. When the perturbation becomes static, the wave function so obtained does not satisfy the time-dependent Schr"odinger equation, and the perturbation equations cannot be reduced to the ordinary time-independent perturbation equations. To remove these difficulties, we introduce a perturbed time-dependent phase factor in deriving a new set of perturbation equations. We then construct the variation-perturbation functionals as in the previous theory; the perturbed wave functions are solved by minimizing these functionals. The same method is also applied to many-electron systems, using the coupled and uncoupled Hartree-Fock scheme.
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 Dirac variation-of-constants method has long provided a basis for perturbative solution of the time-dependent Schr\"odinger equation. In spite of its widespread utilization, certain aspects of the method have been discussed only superficially and remain somewhat obscure. The present review attempts to clarify some of these points, particularly those related to secular and normalization terms. Secular terms arise from an over-all time-dependent phase in the wave function, while normalization terms preserve the norm of the wave function. A proper treatment of the secular terms is essential in the presence of a physically significant level shift that can produce secular divergences in the time-dependent perturbation functions. The normalization terms are always important, although the formulation of a simple method for including them is of greatest utility in applications requiring higher-order perturbation theory (e.g., nonlinear optical phenomena), where difficulties have arisen in previous treatments. Although the Dirac perturbation technique includes the correct secular and normalization terms when properly executed, it is convenient to reinterpret the perturbation problem so that the secular and normalization terms can be factored from the wave function to all orders. It is shown that an appropriate over-all multiplicative, time-dependent normalization and phase factor can be obtained, and that it is simply the amplitude for finding the system in the unperturbed eigenstate at any time ttt. The regular part of the wave function remaining after this factorization provides a complete description of the physical properties of the system of interest and determines the over-all normalization and phase, as well. Most important, the regular function and its perturbation expansion satisfy equations which are more convenient for computational applications than are the customary Dirac equations, and, in contrast to the latter, they reduce directly to the familiar time-independent perturbation equations in the static limit. To illustrate the general development, the model problem of a linearly perturbed harmonic oscillator and the static, harmonic, and electromagnetic perturbations of arbitrary quantum-mechanical systems are treated explicitly. In the case of an adiabatically applied static perturbation, the familiar adiabatic theorem is recovered with the over-all phase factor giving the perturbed eigenvalue, while in the case of an harmonic perturbation, the overall phase factor obtained includes the system level shift appropriate for a quasiperiodic state. For an electromagnetic perturbation, compact expressions are obtained for various nonlinear optical susceptibilities in forms suitable for computations. Time-dependent Hartree-Fock approximations are treated explicity to demonstrate that difficulties can arise when normalization and secular terms are not extracted prior to application of the perturbation formalism. Connection is also made with other methods which can be employed to eliminate secular and normalization terms from the wave function; these include a projection procedure and multiple-time-scales perturbation theory. The elimination of secular divergences from the perturbation functions is shown to be important for the construction of a valid Fourier transform. Secular and normalization terms also arise in connection with variational principles for the time-dependent Schr\"odinger equation. By employing the Frenkel variational principle and an ansatz for the total wave function that explicitly isolates the secular and normalization terms, a computationally convenient variational functional is obtained. This form of the Frenkel principle provides a bound to the system level shift induced by an oscillatory perturbation and is equivalent to the Ritz variational principle in the static limit. Explicit expressions for the variational functional in the Hartree-Fock approximations are derived in forms suitable for computational applications to the interactions of radiation and matter.
The many-body wave function of a system of interacting particles confined by a time-dependent harmonic potential and perturbed by a time-dependent spatially homogeneous electric field is derived via the Feynman path-integral method. The wave function is comprised of a phase factor times the solution to the unperturbed time-dependent Schrödinger equation with the latter being translated by a time-dependent value that satisfies the classical driven equation of motion. The wave function reduces to that of the Harmonic Potential Theorem wave function for the case of the time-independent harmonic confining potential.