Dirac molecular orbital calculations on both molecules indicate that spin-orbit coupling splits the 2t2 and 3t2 MOs into the 2e″⊕2u′ (2e″ > 2u′) and 4u′⊕3e″ (4u′ > 3e″) relativistic counterparts, due to the small metal contents of the nd 3 2 and nd 5 2 spinors, and of the (n+1)p 3 2 and (n+1)p 1 2 spinors, respectively. The unusual broad band E could be assigned to ionizations arising from a group of relativistic orbitals (3q, 2e3 and 2q) with significant nd 5 2 and nd 3 2 metal contents. The calculated spin-orbit and valence bandwidth values are in good agreement with resolved PES data.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry