A. Muller et al., ELECTRONIC-STRUCTURE OF THIOMETALATES [MS4](N-) (M=MO, W, RE) - XANESSPECTRA AND SCF-X-ALPHA-SW CALCULATIONS, Chemical physics letters, 225(4-6), 1994, pp. 359-363
Sulfur K-edge XANES spectra of PPh4+ salts of the title species are re
ported. Assignments for the characteristic positions in the spectra ar
e given and discussed. The energies of the pre-edge peaks and the main
absorption edges are used to determine the ''crystal-field' splitting
energies DELTA, i.e. the energy difference between the 2e and 4t2 lev
els (1.4 eV for [ReS4]-, 1.1 eV for [WS4]2-and [MoS4]2-) and the energ
ies of some frontier orbitals (HOMO-LUMO region). These data are compa
red with results from Xalpha calculations, electronic absorption and E
SCA spectra.