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 language | English |
|---|---|
| Pages (from-to) | 3252-3260 |
| Number of pages | 9 |
| Journal | Journal of Physical Chemistry |
| Volume | 92 |
| Issue number | 11 |
| Publication status | Published - 1988 |
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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 journal › Article
}
TY - JOUR
T1 - Mean-field models for molecular states and dynamics
T2 - New developments
AU - Gerber, R. B.
AU - Ratner, Mark A
PY - 1988
Y1 - 1988
N2 - 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.
AB - 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.
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M3 - Article
VL - 92
SP - 3252
EP - 3260
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 11
ER -