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On the nature of the lowest excited state of Cr4+-doped olivines

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Publication Date
Volume
234
Identifiers
DOI: 10.1016/0009-2614(95)00063-a
Disciplines
  • Mathematics

Abstract

Abstract A Franck-Condon and ligand field analysis of published spectral data are used to characterize the lowest excited state of Cr 4+ at the distorted tetrahedral sites in Ca 2GeO 4 as dominated by a split component of the 3T 2 term, with a negligibly small 1E admixture, in contrast to Mg 2SiO 4 (forsterite), where a roughly 1:1 3T 2 and 1E mixing is found. The small changes in the CrO equilibrium geometry on excitation, as reflected by the most prominent 0-0 line in both matrices result from the large stretching mode force constant which outweighs the vibronic force upon exciting from e 2 (ground state) to e 1t 2 1 (excited state). The broad-band low-temperature emission in some Cr 4+-doped olivines is assigned to bending modes which become active for sufficiently large geometric distortions.

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