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Ligand polarisability derivatives and anisotropies in the theory of f—f vibronic intensities

✍ Scribed by Brian Stewart

Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
516 KB
Volume
206
Category
Article
ISSN
0009-2614

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✦ Synopsis

Hitherto neglected terms are introduced into the theory of vibronic transition intensities in f-f spectra. Ligand polarisability derivatives and anisotropies make important contributions to the emission intensity for the 'Do-+&, us WansitionofoctahedraIly coordinated Eu'"') in the elpasolite CslNa [EuClJ. The terms involving derivatives of mean bond polarisabilities and of bond polarisability anisotropies are comparable in magnitude but antagonistic to those arising from the derivatives of the quadrupoledipole coupling tensor for the radial stretching mode considered. The bond polarisability derivative terms predict significant intensity to arise from locally Raman-active modes in polyatomic ligands at longer range.

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