Ab initio studies of the electronic structure and geometry of UF/sub 5/ using relativistic effective core potentials
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Ab initio calculations on the low-lying electronic states of UF/sub 5/ are presented using a relativistic effective core potential (ECP) for uranium and a nonrelativistic ECP for fluorine. The ground-state geometry of UF/sub 5/ was optimized at the SCF level using a double-zeta quality Gaussian basis set. Without spin-orbit coupling the square pyramidal structure (C/sub 4v/) was calculated to be 1 kcal/mol lower than the trigonal bipyramid (D/sub 3h/), which was subject to a Jahn-Teller distortion. Inclusion of spin-orbit effects reversed the ordering with the D/sub 3h/ structure 1 kcal/mol lower than the C/sub 4v/. The two geometries are connected by a monotonic C/sub 2v/ path, so that UF/sub 5/ will be fluxional. The ramifications of this fluxional behavior are considered. Improved virtual orbital calculations show that UF/sub 5/ has a series of weak low-lying (2 - 15 x 10/sup 3/ cm/sup -1/)f-f transitions. The results of the photofragment spectra of UF/sub 6/ are discussed in light of these calculations. 44 references, 7 figures, 7 tables.
- Research Organization:
- Los Alamos Scientific Lab., NM
- OSTI ID:
- 5878679
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:18; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Journal Article
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Wed Aug 15 00:00:00 EDT 1979
· J. Chem. Phys.; (United States)
·
OSTI ID:6096512
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Journal Article
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Sat Dec 31 23:00:00 EST 1983
· J. Chem. Phys.; (United States)
·
OSTI ID:5457836
Thermochemistry of gaseous UF/sub 5/ and UF/sub 4/
Journal Article
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Wed Jun 01 00:00:00 EDT 1977
· J. Chem. Phys.; (United States)
·
OSTI ID:7313674
Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
CALCULATION METHODS
CHEMICAL BONDS
COUPLING
DATA
DATA FORMS
ELECTRIC POTENTIAL
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
GEOMETRY
GROUND STATES
HALIDES
HALOGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INTERMEDIATE COUPLING
L-S COUPLING
MATHEMATICAL MODELS
MATHEMATICS
NUMERICAL DATA
NUMERICAL SOLUTION
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TABLES
URANIUM COMPOUNDS
URANIUM FLUORIDES
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
CALCULATION METHODS
CHEMICAL BONDS
COUPLING
DATA
DATA FORMS
ELECTRIC POTENTIAL
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
GEOMETRY
GROUND STATES
HALIDES
HALOGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INTERMEDIATE COUPLING
L-S COUPLING
MATHEMATICAL MODELS
MATHEMATICS
NUMERICAL DATA
NUMERICAL SOLUTION
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TABLES
URANIUM COMPOUNDS
URANIUM FLUORIDES