ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
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 Ag3. Coupling parameters obtained for a simultaneous fit to absorption and emission results are k=1.93, g=0.25 for the E' ground state and k=0.19, g=0.02 for the E‘ 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.467093
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