Premium
Relativity and the chemistry of UF 6 : A molecular Dirac—Hartree—Fock—CI study
Author(s) -
De Jong W. A.,
Nieuwpoort W. C.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)58:2<203::aid-qua9>3.0.co;2-1
Subject(s) - spinor , relativistic quantum chemistry , ionic bonding , chemistry , theory of relativity , molecule , bond dissociation energy , electronic structure , valence (chemistry) , atomic physics , quantum chemistry , physics , quantum mechanics , theoretical physics , ion , computational chemistry , supramolecular chemistry
The electronic structure and bonding of UF 6 and UF 6 − are studied within a relativistic framework using the MOLFDIR program package. A stronger bonding but more ionic molecule is found if one compares the relativistic with the nonrelativistic results. The first peak in the photoelectron spectrum of Karlsson et al. is assigned to the 12γ 8 u component of the 4 t 1 u orbital, in agreement with other theoretical and experimental results. Good agreement is found between the experimental and theoretical 5 f spectrum UF 6 − . Some properties, like the dissociation energy and electron affinity, are calculated and the necessity of a fully relativistic framework is shown. The Breit interaction has an effect on the core spinors and the spin‐orbit splitting of these spinors but the influence on the valence spectrum is negligible. © 1996 John Wiley & Sons, Inc.