Mean-field models for molecular states and dynamics

New developments

R. B. Gerber, Mark A Ratner

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

For accurate description of vibration/rotation eigenstates of molecules, and for discussion of reactions and relaxation processes, simple independent-mode pictures are generally inadequate. Mean-field methods, in which each mode acts subject to a mean potential (static or dynamic) that is just the exact potential averaged over all other modes of the system, are attractive for treating such problems for several reasons: they are conceptually simple, numerically tractable, quantitatively quite accurate, and generally applicable to a wide variety of molecular species, energies, and coupling conditions. For these reasons, such mean-field, or self-consistent-field, techniques have been applied to molecular problems quite extensively within the last decade. We discuss several aspects of recent and current work on mean-field applications to molecular problems. In the class of static mean-field, or self-consistent-field, methods such situations include inversion of vibration/ rotation spectra to obtain potential energy surfaces, distorted-wave Born approximation work on vibrational predissociation lifetimes of long-lived van der Waals complexes, and an extension of the Slater theory for unimolecular decay rates in the weak-coupling regime. Applications of time-dependent SCF, or TDSCF, include a linearized approximation for investigation of long-time processes and study of the Fourier representation to derive random-phase approximations for direct calculation both of excitation energies and of instabilities and lifetimes. Several intriguing problems remain in the general area of mean-field methods for molecular systems: these include optimal choice of coordinate systems, selection of initial state in dynamical problems, and methods for tractable extension of mean-field approximations.

Original languageEnglish
Pages (from-to)3252-3260
Number of pages9
JournalJournal of Physical Chemistry
Volume92
Issue number11
Publication statusPublished - 1988

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Born approximation
Potential energy surfaces
Excitation energy
Relaxation processes
Surface waves
self consistent fields
Molecules
approximation
life (durability)
vibration
surface waves
decay rates
eigenvectors
potential energy
inversions
energy
excitation
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Mean-field models for molecular states and dynamics : New developments. / Gerber, R. B.; Ratner, Mark A.

In: Journal of Physical Chemistry, Vol. 92, No. 11, 1988, p. 3252-3260.

Research output: Contribution to journalArticle

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