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Title: 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:
;  [1]; ; ;  [2]
  1. Department of Chemistry, Purdue University, West Lafayette, Indiana 47907 (United States)
  2. 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}
}