A simple model for correcting the zero point energy problem in classical trajectory simulations of polyatomic molecules

William H. Miller, William L. Hase, Cynthia L. Darling

Research output: Contribution to journalArticlepeer-review

178 Scopus citations

Abstract

A simple model is proposed for correcting problems with zero point energy in classical trajectory simulations of dynamical processes in polyatomic molecules. The "problems" referred to are that classical mechanics allows the vibrational energy in a mode to decrease below its quantum zero point value, and since the total energy is conserved classically this can allow too much energy to pool in other modes. The proposed model introduces hard sphere-like terms in action-angle variables that prevent the vibrational energy in any mode from falling below its zero point value. The algorithm which results is quite simple in terms of the cartesian normal modes of the system: if the energy in a mode k, say, decreases below its zero point value at time t, then at this time the momentum Pk for that mode has its sign changed, and the trajectory continues. This is essentially a time reversal for mode k (only!), and it conserves the total energy of the system. One can think of the model as supplying impulsive "quantum kicks" to a mode whose energy attempts to fall below its zero point value, a kind of "Planck demon" analogous to a Brownian-like random force. The model is illustrated by application to a model of CH overtone relaxation.

Original languageEnglish
Pages (from-to)2863-2868
Number of pages6
JournalThe Journal of Chemical Physics
Volume91
Issue number5
DOIs
StatePublished - 1989

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