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The Journal of Chemical Physics

Multidimensional wave functions from classical trajectories

Michael J. Davis, Eric J. Heller

Published Oct 15, 1981• 98 citations
Publisher

Abstract

A new technique is developed to generate semiclassical wave functions. The method uses only information already available from a standard semiclassical quantization of a system. Linear superpositions of Gaussian coherent states that lie along quantizing classical trajectories are used, with phases given by the action integrals plus a Maslov-type correction. Wave functions generated in this way suffer from none of the problems with caustics that primitive semiclassical wave functions encounter. The semiclassical wave functions are convenient for subsequent use in applications, e.g., molecular spectra. By generating wave functions for several simple systems, we show that under most circumstances these wave functions are very accurate approximations to the true quantum states.

DOI
10.1063/1.442548

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A new technique is developed to generate semiclassical wave functions. The method uses only information already available from a standard semiclassical quantization of a system. Linear superpositions of Gaussian coherent states that lie along quantizing classical trajectories are used, with phases given by the action integrals plus a Maslov-type correction. Wave functions generated in this way suffer from none of the problems with caustics that primitive semiclassical wave functions encounter. The semiclassical wave functions are convenient for subsequent use in applications, e.g., molecular spectra. By generating wave functions for several simple systems, we show that under most circumstances these wave functions are very accurate approximations to the true quantum states.
The semiclassical theory developed by Maslov and Fedoriuk is used to calculate the wave function for a two-dimensional bound state system. We investigate in detail an eigenstate of a coupled anharmonic oscillator system. The primitive semiclassical wave function is obtained from the characteristic function S and the density function J. Each of these functions consists of four branches corresponding to the four possible directions of motion of the classical trajectory through any point. The interference from the four branches determines the basic structure of the wave function. A uniform approximation gives a wave function which is well behaved along each caustic and which is in good agreement with the fully quantal wave function.
The globally uniform semiclassical approximation for energy eigenstates developed by D. Zor and K. G. Kay [Phys. Rev. Lett. 76, 1990 (1996)] is derived explicitly for the case of multidimensional systems and is applied to two test cases. The adiabatic switching approximation is used to obtain various quantities that enter the semiclassical expression. Two formulations of the method are examined: one requiring several trajectories for each desired state and another requiring only a single trajectory per state. The multitrajectory version yields accurate results for all states investigated (overlap between semiclassical and quantum eigenstates >0.98), including some influenced by classical chaos. The single-trajectory treatment, however, is more efficient, gives accurate results for regular states, and is even applicable for certain chaotic states, although the multiple-trajectory method is preferred in such cases. Despite the substantial resemblance of the present theory to the frozen Gaussian approximation (FGA), it is a true semiclassical approximation and is found to produce wave functions that are significantly more accurate than those obtained from the FGA for all states examined.
We present in this paper a coordinate independent semiclassical quantization method. We demonstrate that in order to extract accurate eigenvalues and eigenfunctions the trajectory does not necessarily have to reside on the quantizing torus, rather, one can use information obtained on arbitrary tori. Because the method is coordinate independent, no difficulty is encountered in quantizing within classical resonance zones. Furthermore, nearby eigenstates and eigenvalues (nearby in action space) may be extracted from the same trajectory—this is especially convenient when the density of states becomes large.
We examine semiclassical propagation of nonstationary states. The fundamental object is the 1928 time dependent Van Vleck semiclassical Green`s function, as modified by Gutzwiller in 1967. This direct approach to semiclassical quantum mechanics has received very little attention over the years. The problems of evaluating the Green`s function (finding all trajectories which go from x{prime} to x in time t, for every x, x{prime}, and t sounds foreboding) and the development of caustics at an alarming rate in chaotic systems, may have suppressed its use. We have developed several strategies for evaluating it efficiently, including for chaotic dynamics. We found it can be used to accurately propagate smooth wave functions in spite of the caustics. The smooth wave function has the effect of strongly damping the caustics and leaving an accurate propagated state. Moreover many of the contributions to the semiclassical amplitude are legal, and allow a much longer time scale for breakdown of the semiclassical propagation than had previously been thought. This has allowed us to extract accurate spectra and eigenstates for chaotic dynamics in the stadium billiard and to calculate a complete molecular electronic absorption spectrum for two nonlinearly interacting vibrational modes, including line intensities and positions, usingmore » only classical trajectory input.« less
This paper reports a method to build a semiclassical wave function corresponding to an invariant torus satisfying Einstein-Brillouin-Keller quantization conditions. Instead of calculating the stability matrix of the trajectory at each step, as in the standard method of Keller [Ann. Phys. (N.Y.) 4, 180 (1958)] or the modification of Maslov and Fedoriuk [Semiclassical Approximations in Quantum Mechanics (Reidel, Dordrecht, 1981)], we use the actual density of the trajectory, calculated by running the trajectory and counting passages through cells in coordinate space. The method is tested for a system of coupled Morse oscillators, and found to be comparable in accuracy to the standard method. It may be more useful than the standard method for testing ideas for semiclassical quantization in the chaotic regime.
A new method is proposed for constructing approximate solutions to the Schrödinger equation. In place of the wave function, its Gaussian-windowed Fourier transform is used as the fundamental entity. This allows an intuitively attractive connection to be made with a family of classical trajectories and, at all times, the wave function is inferred from the present state of these trajectories. The fact that the connection between the wave function and the classical trajectories is consistently constructed in phase space allows this method to be free of the limitations of other methods.