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The Journal of Chemical Physics

High-Order Time-Dependent Perturbation Theory for Classical Mechanics and for Other Systems of First-Order Ordinary Differential Equations

R. A. Marcus

Published May 1, 1970• 16 citations
Publisher

Abstract

A time-dependent perturbation solution is derived for a system of first-order nonlinear or linear ordinary differential equations. By means of an ansatz, justified a posteriori, the latter equations can be converted to an operator equation which is solvable by several methods. The solution is subsequently specialized to the case of classical mechanics. For the particular case of autonomous equations the solution reduces to a well-known one in the literature. However, when collision phenomena are treated and described in a classical “interaction representation” the differential equations are typically nonautonomous, and the more general solution is required. The perturbation expression is related to a quantum mechanical one and will be applied subsequently to semiclassical and classical treatments of collisions.

DOI
10.1063/1.1673715

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A time-dependent perturbation solution is derived for a system of first-order nonlinear or linear ordinary differential equations. By means of an ansatz, justified a posteriori, the latter equations can be converted to an operator equation which is solvable by several methods. The solution is subsequently specialized to the case of classical mechanics. For the particular case of autonomous equations the solution reduces to a well-known one in the literature. However, when collision phenomena are treated and described in a classical “interaction representation” the differential equations are typically nonautonomous, and the more general solution is required. The perturbation expression is related to a quantum mechanical one and will be applied subsequently to semiclassical and classical treatments of collisions.
We propose a unified approach for different exponential perturbation techniques used in the treatment of time-dependent quantum mechanical problems, namely the Magnus expansion, the Floquet–Magnus expansion for periodic systems, the quantum averaging technique, and the Lie–Deprit perturbative algorithms. Even the standard perturbation theory fits in this framework. The approach is based on carrying out an appropriate change of coordinates (or picture) in each case, and it can be formulated for any time-dependent linear system of ordinary differential equations. All of the procedures (except the standard perturbation theory) lead to approximate solutions preserving by construction unitarity when applied to the time-dependent Schrödinger equation.
We propose a unified approach for different exponential perturbation techniques used in the treatment of time-dependent quantum mechanical problems, namely the Magnus expansion, the Floquet--Magnus expansion for periodic systems, the quantum averaging technique and the Lie--Deprit perturbative algorithms. Even the standard perturbation theory fits in this framework. The approach is based on carrying out an appropriate change of coordinates (or picture) in each case, and can be formulated for any time-dependent linear system of ordinary differential equations. All the procedures (except the standard perturbation theory) lead to approximate solutions preserving by construction unitarity when applied to the time-dependent Schrödinger equation.
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.
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.
An alternative method is proposed for deriving the time dependent Schroedinger equation from the pictures of wave and matrix mechanics. The derivation is of a mixed classical quantum character, since time is treated as a classical variable, thus avoiding any controversy over its meaning in quantum mechanics. The derivation method proposed in this paper requires no ad hoc assumption and avoids going through a second-order differential equation that can be reduced to the well known time-dependent Schroedinger equation only postulating a complex wavefunction with an exponential time dependence, as did by Schroedinger in its original paper of 1926.
The treatment of Schrödinger's perturbation theory based on the use of a series of inhomogeneous differential equations of iterative character is briefly surveyed. As an illustration, the method is used to derive the general expression for the expectation value of the Hamiltonian to any order which provides an upper bound for the ground-state energy. It is indicated how the well-known theory for inhomogeneous equations may be utilized also in this special case. The solution of the Schrödinger equation by means of the partitioning technique and the concept of reduced resolvents is then treated. It is shown that the expressions obtained are most conveniently interpreted in terms of inhomogeneous differential equations. A study of the connection with the first approach reveals that the two methods are essentially equivalent, but also that the use of reduced resolvents and inverse operators may give an alternative insight in the mathematical structure of perturbation theory, particularly with respect to the ``bracketing theorem'' and the use of power series expansions with a remainder. In conclusion, it is emphasized that the combined use of the two methods provides a simpler and more powerful tool than any one of them taken separately.