Ab initio studies of excited states of polyatomic molecules including spin-orbit and multiplet effects: The electronic states of UF/sub 6/

Journal Article · Thu Dec 01 04:00:00 EST 1983 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.445665· OSTI ID:5667380

Hay, P J

The excited electronic states of UF/sub 6/ between 3--10 eV are investigated by ab initio configuration interaction (CI) calculations using a relativistic effective core potential (RECP) on the uranium and nonrelativistic ECP's on the fluorines. Spin-orbit coupling effects are incorporated by diagonalizing an effective one-electron operator over the CI wave functions. This represents one of the first studies of polyatomic molecules to treat both spin-orbit effects and multiplet effects arising from electron--electron interactions. A detailed analysis of the electronic states of UF/sub 6/ is given both with and without spin-orbit coupling effects. Assignments for the major peaks in the 3--10 eV energy range are given, as aided by recent electron impact studies. Comparisons are made between the present many-electron states and previous one-electron theoretical treatments.

• Research Organization: Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
• OSTI ID: 5667380
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 79:11; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTINIDE COMPOUNDS
COLLISIONS
CONFIGURATION INTERACTION
COUPLING
ELECTRON COLLISIONS
ELECTRON-MOLECULE COLLISIONS
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INTERMEDIATE COUPLING
L-S COUPLING
MOLECULE COLLISIONS
URANIUM COMPOUNDS
URANIUM FLUORIDES
URANIUM HEXAFLUORIDE