On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]
Abstract
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.
- Authors:
-
- Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (United States)
- Department of Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
- Publication Date:
- OSTI Identifier:
- 5002094
- DOE Contract Number:
- FG09-90ER14156
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics; (United States)
- Additional Journal Information:
- Journal Volume: 100:9; Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; 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-)
Citation Formats
Wedum, E E, Grant, E R, Cheng, P Y, Willey, K F, and Duncan, M A. On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]. United States: N. p., 1994.
Web. doi:10.1063/1.467093.
Wedum, E E, Grant, E R, Cheng, P Y, Willey, K F, & Duncan, M A. On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]. United States. https://doi.org/10.1063/1.467093
Wedum, E E, Grant, E R, Cheng, P Y, Willey, K F, and Duncan, M A. 1994.
"On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]". United States. https://doi.org/10.1063/1.467093.
@article{osti_5002094,
title = {On the assignment of Jahn--Teller effects in the ultraviolet absorption spectrum of Ag[sub 3]},
author = {Wedum, E E and Grant, E R and Cheng, P Y and Willey, K F and Duncan, M A},
abstractNote = {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.},
doi = {10.1063/1.467093},
url = {https://www.osti.gov/biblio/5002094},
journal = {Journal of Chemical Physics; (United States)},
issn = {0021-9606},
number = ,
volume = 100:9,
place = {United States},
year = {Sun May 01 00:00:00 EDT 1994},
month = {Sun May 01 00:00:00 EDT 1994}
}