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Molecular dynamics with electronic transitions

J. Chem. Phys. 93, 1061 (1990); doi:10.1063/1.459170

Issue Date: 15 July 1990

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John C. Tully
AT&T Bell Laboratories, Murray Hill, New Jersey 07974
A method is proposed for carrying out molecular dynamics simulations of processes that involve electronic transitions. The time dependent electronic Schrödinger equation is solved self-consistently with the classical mechanical equations of motion of the atoms. At each integration time step a decision is made whether to switch electronic states, according to probabilistic ``fewest switches'' algorithm. If a switch occurs, the component of velocity in the direction of the nonadiabatic coupling vector is adjusted to conserve energy. The procedure allows electronic transitions to occur anywhere among any number of coupled states, governed by the quantum mechanical probabilities. The method is tested against accurate quantal calculations for three one-dimensional, two-state models, two of which have been specifically designed to challenge any such mixed classical–quantal dynamical theory. Although there are some discrepancies, initial indications are encouraging. The model should be applicable to a wide variety of gas-phase and condensed-phase phenomena occurring even down to thermal energies. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 24 January 1990; accepted 2 April 1990
Permalink: http://link.aip.org/link/?JCPSA6/93/1061/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.10.Cs
    Molecular spectra and interactions of molecules with photons Calculation of molecular spectra Calculational methods (including new theoretical techniques and applications of group theory)
  • YEAR: 1990

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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