X-RAY SPECTRAL DETERMINATION OF THE EFFECTIVE CHARGES ON PHOSPHORUS, SULFUR, AND CHLORINE ATOMS IN CHEMICAL-COMPOUNDS WITH A NONEMPIRICAL CHARGE SCALE

Linear dependence between the experimental K-a line shifts and Mullike n atomic charges obtained by SCF ab initio calculations with 4-31G, 4- 31G: and 4-31G* basis sets for the P, S, and CZ atoms have been found . The electron density redistribution of PCl3 and SPCl3 free ligands o n their complexation with AlBr3 has been investigated lt has been show n that a significant transfer of the total ligand electron density to the acceptor is absent, but there is an essential growth of the ionici ty of all bonds on complexation. The P=S and P-S bond ionicities are f ound to increase linearly with the growth of the positive charge on th e central phosphorus atom. (C) 1996 John Wiley & Sons, Inc.