Open AccessJournal Article
Ab initio studies of the electronic structure of UF6, UF6/+/, and UF6/-/ using relativistic effective core potentials
TLDR
In this article, the relativistic effective core potential (ECP) for uranium and a nonrelativistic ECP for fluorine was used to calculate the electron affinity of UF6 (7.1 eV).Abstract:
The paper presents ab initio calculations performed on the electronic states of UF6, UF6(+), and UF6(-) using a relativistic effective core potential (ECP) for uranium and a nonrelativistic ECP for fluorine. In most of the calculations 56 valence electrons are treated explicitly using a contracted (3s 3p 2d 2f/2s2p) Gaussian basis. It is noted that various ECP's were explored, but all yield an overall charge density of U(+2.4)/F(-0.4)/6. In addition, the bonding in the ground state of UF6 is discussed. SCF and CI calculations on UF6(+) are compared with the experimental photoelectron spectrum and with previous scattered wave calculations. Further, the role of spin-orbit coupling in the states of UF6(+) and UF6(-) is covered. Finally, it is concluded that the calculated electron affinity of UF6 (7.1 eV) is considerably larger than in current experimental estimates, but the relative energies of the states of UF6(-) are in agreement (0.1-0.2 eV) with those of the experiment.read more
Citations
More filters
Journal ArticleDOI
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
Willard R. Wadt,P. Jeffrey Hay +1 more
TL;DR: In this article, a consistent set of ab initio effective core potentials (ECP) has been generated for the main group elements from Na to Bi using the procedure originally developed by Kahn.
Lecture notes in Chemistry
TL;DR: The Lecture Notes in Chemistry (LNC) series as discussed by the authors provides an accessible introduction to the field to postgraduate students and nonspecialist researchers from related areas, providing a source of advanced teaching material for specialized seminars, courses and schools, and being readily accessible in print and online.
Book ChapterDOI
Electronic structure and bonding in actinyl ions
TL;DR: In this paper, the Inverse trans influence is introduced in the context of the actinide-oxygen bond and the experimental energy level scheme is compared with the results of molecular orbital calculations of varying degrees of sophistication, the most successful being SCF calculations incorporating the effects of relativity.
Journal ArticleDOI
First experimental photoelectron spectra of superhalogens and their theoretical interpretations
TL;DR: In this paper, photo-electron spectra of the MX2− superhalogen anions have been obtained for the first time, and the first vertical detachment energies (VDEs) were measured to be 5.92±0.04 (LiCl2−), 5.86± 0.06 (NaCl2+ ), 5.42±0, 5.88±0., 4.84± 0, 4.57 (LiI2+), and 4.50 eV (NaI2−) in excellent agreement with the experimental values
Journal ArticleDOI
Density functional calculations on actinide compounds: Survey of recent progress and application to [UO2X4]2− (X=F, Cl, OH) and AnF6 (An=U, Np, Pu)
TL;DR: In this article, the application of density functional theory (DFT) to molecular systems containing actinide elements is discussed in two parts, covering the time from about 1991 to the present.
References
More filters
Journal ArticleDOI
Approximate relativistic corrections to atomic radial wave functions
TL;DR: The mass-velocity and Darwin terms of the one-electron-atom Pauli equation have been added to the Hartree-Fock differential equations by using the HX formula to calculate a local central field potential for use in these terms as discussed by the authors.
Journal ArticleDOI
Triplet‐Singlet Transitions in Organic Molecules. Lifetime Measurements of the Triplet State
TL;DR: In this paper, the emission lifetimes of the metastable triplet states (phosphorescent states) of a large variety of organic molecules have been measured and it is shown that the transition probabilities corresponding to shorter lifetimes are of the same magnitude as found in the light atoms of which the molecule is composed.
Journal ArticleDOI
Excited States of H2O using improved virtual orbitals
TL;DR: In this paper, a technique for solving the Hartree-Fock equations is proposed which has the property that the virtual orbitals from the ground state wavefunction are variationally correct approximations to the self-consistent orbitals for the excited states.
Related Papers (5)
Relativity and the chemistry of UF6: A molecular Dirac-Hartree-Fock-CI study
W. A. De Jong,W.C. Nieuwpoort +1 more