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