skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Theoretical studies on the physical properties and bonding of the 5d metal hexafluorides using the multiple scattering X. cap alpha. technique

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00533a007· OSTI ID:5051567

Nonrelativistic overlapping spheres X..cap alpha.. multiple scattering OSMSX..cap alpha.. calculations have been performed on the 5d heavy metal hexafluorides MF/sub 6/, where M = W, Re, Os, Ir, Pt, and Au, and on MoF/sub 6/ and SF/sub 6/. With the aid of these calculations a consistent interpretation of the ionization potentials (IPs), electron affinities (EAs), and charge transfer (CT) electronic absorption bands for these molecules is obtained. The calculations are also shown to be successful in interpreting molecular properties related to the charge-density distributions. The method is found to be very useful in predicting trends in all the properties across the 5d series. Relativistic effects are discussed, and for the EAs it is found necessary to take into account these effects. After a semiempirical correction factor of approx. 1.0 eV, deduced from the molecular spin-orbit coupling constants is applied, the EAs are found to agree well with the most recent experimental estimates.

Research Organization:
Univ. of Tennessee, Knoxville
OSTI ID:
5051567
Journal Information:
J. Am. Chem. Soc.; (United States), Vol. 102:13
Country of Publication:
United States
Language:
English