On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]

Journal Article · Sun May 01 04:00:00 EDT 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.467093· OSTI ID:5002094

Wedum, E E; Grant, E R ^[1]; Cheng, P Y; Willey, K F; Duncan, M A ^[2]

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1. Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (United States)
2. 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), Journal Name: Journal of Chemical Physics; (United States) Vol. 100:9; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664200 -- Spectra of Atoms & Molecules & their Interactions with Photons-- (1992-)
664500* -- Special Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
COUPLING
ELEMENTS
EMISSION SPECTRA
ENERGY LEVELS
EXCITED STATES
HAMILTONIANS
INTERMEDIATE COUPLING
JAHN-TELLER EFFECT
L-S COUPLING
MATHEMATICAL OPERATORS
METALS
QUANTUM OPERATORS
SILVER
SPECTRA
TRANSITION ELEMENTS
ULTRAVIOLET SPECTRA
VIBRATIONAL STATES