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

Autor:	N. Roesch, A. Goerling, Graham A. Bowmaker, O. Haeberlen, D.E. Ellis, G.L. Goodman
Rok vydání:	1992
Předmět:	chemistry.chemical_classification Order (ring theory) Electronic structure Electron spectroscopy Inorganic Chemistry Bond length Crystallography Molecular geometry chemistry Computational chemistry Molecular orbital Physical and Theoretical Chemistry Ionization energy Inorganic compound
Zdroj:	Inorganic Chemistry. 31:577-581
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic00030a010
Popis:	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.
Databáze:	OpenAIRE
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