THEORETICAL STUDY OF THE EFFECTS OF SPIN-ORBIT COUPLING ON THE VALENCE PHOTOELECTRON SPECTRUM OF HFCL4

摘要

The ground state valence electronic structure and ionisation energies of HfCl4, are calculated using quasi-relativistic local density functional theory. The optimised Hf-CI bond length exactly matches the experimentally determined value. The calculated ionisation energies are ca. 0.5-0.7 eV lower than the experimental, and suggest a reversal of the assignment of bands c and d in the photoelectron spectrum. The 0.14 eV separation of the fine structure of band b is reproduced exactly, and is traced to spin-orbit coupling in the parent t(2), molecular orbital. This spin-orbit splitting is due to a metal p atomic orbital contribution to the t(2) orbital. (C) 1997 Published by Elsevier Science B.V. [References: 35]