Published February 1984
| public
Journal Article
Semiclassical and Quantum Vibrational Intensities
- Creators
- Wardlaw, D. M.
- Noid, D. W.
-
Marcus, R. A.
Abstract
The semiclassical theory of infrared vibrational intensities is extended and applied to multidimensional systems. The validity and utility of the semiclassical approach is assessed by comparison with perturbative and exact quantum results for one nonresonant and two resonant model Hamiltonian systems. Approximate mean trajectories are found to provide intensities accurate to within ~20% and frequencies accurate to within ~ 1% for almost all transitions studied. More accurate semiclassical results can be obtained by using exact mean trajectories and, for intensities in the nonresonant system, trajectories determined by an improved correspondence rule. The advantages and limitations of the semiclassical method are summarized.
Additional Information
© 1984 American Chemical Society. Received August 3, 1983. The research was supported by the U.S. Department of Energy under Contract W-7495-eng-26 with Union Carbide Corporation (at Oak Ridge) and the National Science Foundation (at California Institute of Technology). We thank Dr. M. L. Koszykowski for useful discussions throughout this work.Additional details
- Eprint ID
- 58672
- DOI
- 10.1021/j150647a044
- Resolver ID
- CaltechAUTHORS:20150629-122749538
- W-7495-eng-26
- Department of Energy (DOE)
- NSF
- Created
-
2015-06-29Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 6873