In this paper we develop a new approach to semiclassical dynamics which exploits the fact that extended wavefunctions for heavy particles (or particles in harmonic potentials) may be decomposed into time−dependent wave packets, which spread minimally and which execute classical or nearly classical trajectories. A Gaussian form for the wave packets is assumed and equations of motion are derived for the parameters characterizing the Gaussians. If the potential (which may be nonseparable in many coordinates) is expanded in a Taylor series about the instantaneous center of the (many−particle) wave packet, and up to quadratic terms are kept, we find the classical parameters of the wave packet (positions, momenta) obey Hamilton’s equation of motion. Quantum parameters (wave packet spread, phase factor, correlation terms, etc.) obey similar first order quantum equations. The center of the wave packet is shown to acquire a phase equal to the action integral along the classical path. State−specific quantum information is obtained from the wave packet trajectories by use of the superposition principle and projection techniques. Successful numerical application is made to the collinear He + H2 system widely used as a test case. Classically forbidden transitions are accounted for and obtained in the same manner as the classically allowed transitions; turning points present no difficulties and flux is very nearly conserved.
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Research Article| February 15 1975
Time‐dependent approach to semiclassical dynamics
Special Collection: JCP 90 for 90 Anniversary Collection
J. Chem. Phys. 62, 1544–1555 (1975)
Eric J. Heller; Time‐dependent approach to semiclassical dynamics. J. Chem. Phys. 15 February 1975; 62 (4): 1544–1555. https://doi.org/10.1063/1.430620
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