CALCULATION AND COMPARISON OF ALPHA-VIBRONIC, EPSILON-VIBRONIC AND TAU-VIBRONIC COUPLING-CONSTANTS OF OCTAHEDRAL COORDINATED D-ELECTRON SYSTEMS - CRCL63- AS EXAMPLE

Authors
Citation
K. Wissing et J. Degen, CALCULATION AND COMPARISON OF ALPHA-VIBRONIC, EPSILON-VIBRONIC AND TAU-VIBRONIC COUPLING-CONSTANTS OF OCTAHEDRAL COORDINATED D-ELECTRON SYSTEMS - CRCL63- AS EXAMPLE, Zeitschrift für physikalische Chemie, 200, 1997, pp. 69-76
Citations number
9
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
ISSN journal
09429352
Volume
200
Year of publication
1997
Part
1-2
Pages
69 - 76
Database
ISI
SICI code
0942-9352(1997)200:<69:CACOAE>2.0.ZU;2-J
Abstract
t X (alpha + epsilon + tau)-coupling constants of octahedral transitio n metal complexes are calculated within an electrostatic model. The el ectron-ligand interaction is taken into account by expanding the poten tial energy V-eL into spherical harmonics and differentiating it with respect to the vibrational symmetry coordinates of the molecule. In fi rst order matrix elements of the form [psi(d)\partial derivative V/par tial derivative Q\ psi(d)] are calculated from which coupling constant s, stabilization energies and Huang-Rhys factors are computed. The T-4 (2g) electronic state of [CrCl6](3-) is characterized as mainly distor ted along the totally symmetric and the e(g)-coordinates. Nearly quant itative agreement with results deduced from luminescence spectra is ac hieved.