A molecular orbital study of bonding and ionization energies in pentavalent uranium imide/amide complexes

Journal Article · Wed Feb 19 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00030a010· OSTI ID:7226907

Bowmaker, G A; Goerling, A; Haeberlen, O; Roesch, N ^[1]; Goodman, G L ^[2]; Ellis, D E ^[3]

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1. Technische Univ. Muenchen, Garching (Germany)
2. Argonne National Lab., IL (United States)
3. Northwestern Univ., Evanston, IL (United States)

Discrete variational local density functional (X{alpha}) calculations on the model complexes ((RN)U(NR{sub 2}){sub 3}) (R = H (1), SiH{sub 3} (2)) have been performed in order to investigate the electronic structure of uranium amido/imido complexes. Special emphasis is placed on the energy ordering of the highest lying levels formed by U 5f orbitals and by out-of-plane N 2p{sub {pi}} orbitals. Orbital relaxations are also estimated by studying the fragments NR and NR{sub 2} with R = H and R = SiMe{sub 3} in order to allow a comparison of the model compounds 1 and 2 with the measured photoelectron spectrum of the complex ((Me{sub 3}SiN)U(N(SiMe{sub 3}){sub 2}){sub 3}). The ionization energies corresponding to the N 2p{sub {pi}} MOs are calculated in the order N 2p{sub {pi}} (amido) < N 2p{sub {pi}} (imido). The calculated level ordering is rationalized by comparing the order of the two types of U-N bonds and the charge distributions of the corresponding ligands. Taking the calculated ordering as well as the character of the molecular orbitals into account, a new assignment of the observed photoelectron spectra is given based on a comparison of He I and He II spectra.

• OSTI ID: 7226907
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:4; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry &amp; Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
AMIDES
BINDING ENERGY
BOND ANGLE
BOND LENGTHS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY
IMIDES
INFORMATION
IONIZATION
LENGTH
LIGANDS
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
SCATTERING
SPECTROSCOPY
THEORETICAL DATA
URANIUM COMPLEXES
X-RAY DIFFRACTION