Electronic structure of negative hexafluoride ions of the transition metals in the third series

Journal Article · Sun Sep 01 04:00:00 EDT 1985 · Sov. J. Coordinat. Chem.; (United States)

OSTI ID:6508972

Gutsev, G L; Boldyrev, A I

The electronic structure of the anions HfF/sub 6//sup -/, TaF/sub 6//sup -/, WF/sub 6//sup -/, ReF/sub 6//sup -/, OsF/sub 6//sup -/, IrF/sub 6//sup -/, PtF/sub 6//sup -/, AuF/sub 6//sup -/ and HgF/sub 6//sup -/ has been calculated by the discrete-variation X..cap alpha.. method in an expanded basis of numerical Hartree-Fock functions. The special features of the electronic structure of the series have been analyzed on the basis of a comparison of the composition of molecular orbitals and data from a Mulliken population analysis. The electron affinity of the corresponding neutral systems has been calculated. It has been shown that the value of the electron affinity (EA) depends on the type and composition of the MO accepting the electron and that its behavior along the series is nonmonotonic. The electron affinity decreases sharply upon the transition from HfF/sub 6/ and TaF/sub 6/ to WF/sub 6/, increases monotonically along the series to AuF/sub 6/, and again decreases upon the transition to HgF/sub 6/. All the hexafluorides considered have electron affinities which are greater than the electron affinity of the fluorine atom and may be classified as superhalogens.

• OSTI ID: 6508972
• Journal Information: Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 10:11; ISSN SJCCD
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AFFINITY
ANGULAR MOMENTUM
ATOMIC MODELS
COORDINATION VALENCES
ELECTRONIC STRUCTURE
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
FLUORIDES
FLUORINE COMPOUNDS
GOLD COMPOUNDS
GOLD FLUORIDES
HAFNIUM COMPOUNDS
HAFNIUM FLUORIDES
HALIDES
HALOGEN COMPOUNDS
HARTREE-FOCK METHOD
HIGH SPIN STATES
IONIZATION POTENTIAL
IRIDIUM COMPOUNDS
IRIDIUM FLUORIDES
MATHEMATICAL MODELS
MERCURY COMPOUNDS
MERCURY FLUORIDES
MERCURY HALIDES
MOLECULAR ORBITAL METHOD
OSMIUM COMPOUNDS
OSMIUM FLUORIDES
PARTICLE PROPERTIES
PLATINUM COMPOUNDS
PLATINUM FLUORIDES
REFRACTORY METAL COMPOUNDS
RHENIUM COMPOUNDS
RHENIUM FLUORIDES
RHENIUM HALIDES
SPIN
TANTALUM COMPOUNDS
TANTALUM FLUORIDES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
TUNGSTEN FLUORIDES
VALENCE