On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]
- Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (United States)
- Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
A Jahn--Teller linear-plus-quadratic Hamiltonian is shown to account for most of the observed band positions and intensities in the absorption and emission spectra of Ag[sub 3]. Coupling parameters obtained for a simultaneous fit to absorption and emission results are [ital k]=1.93, [ital g]=0.25 for the [ital E][prime] ground state and [ital k]=0.19, [ital g]=0.02 for the [ital E][double prime] excited state. At higher vibrational energies, simple Jahn--Teller calculations predict fewer bands than observed. Calculations including spin--orbit coupling with larger linear coupling partially quenched by the Ham effect offer a reasonable explanation for this higher energy structure. Splittings and intensity sharing at lower vibrational energies, however, demand higher-order Jahn--Teller coupling, indicating the need for more extensive calculation simultaneously incorporating quadratic Jahn--Teller effects, spin--orbit coupling, and perhaps anharmonicity.
- DOE Contract Number:
- FG09-90ER14156
- OSTI ID:
- 5002094
- Journal Information:
- Journal of Chemical Physics; (United States), Vol. 100:9; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
SILVER
JAHN-TELLER EFFECT
ABSORPTION SPECTRA
COUPLING
EMISSION SPECTRA
HAMILTONIANS
L-S COUPLING
ULTRAVIOLET SPECTRA
VIBRATIONAL STATES
ELEMENTS
ENERGY LEVELS
EXCITED STATES
INTERMEDIATE COUPLING
MATHEMATICAL OPERATORS
METALS
QUANTUM OPERATORS
SPECTRA
TRANSITION ELEMENTS
664500* - Special Atoms & Molecules- (1992-)
664200 - Spectra of Atoms & Molecules & their Interactions with Photons- (1992-)