Combined He I/He II Photoelectron Spectroscopic and Hartree-Fock-Slater Investigation of Electronic Structure and Bonding in Uranium Hexamethoxide

B. E. Bursten; M. Casarin; D. E. Ellis; I. Fragala; T. J. Marks

doi:10.1021/ic00228a037

Combined He I/He II Photoelectron Spectroscopic and Hartree-Fock-Slater Investigation of Electronic Structure and Bonding in Uranium Hexamethoxide

B. E. Bursten, M. Casarin, D. E. Ellis, I. Fragala, T. J. Marks

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Abstract

The electronic structure of the uranium(VI) alkoxide U(OCH₃)₆ has been investigated by using a combination of He I/He II photoelectron spectroscopy and discrete variational (DV) Xa molecular orbital calculations. Good agreement is obtained between the experimental and calculated ionization energies. It is found that the low ionization energy features of the photoelectron spectra are due to varying degrees of donation of the oxygen lone pairs to the empty orbitals on the uranium atom and to the reduction of the molecular symmetry to C_ivia bending of the U-O-C linkages. The methyl groups act as both α and π donors to the oxygen 2p orbitals, increasing the overall donor strength of the alkoxide ligands.

Original language	English (US)
Pages (from-to)	1257-1261
Number of pages	5
Journal	Inorganic chemistry
Volume	25
Issue number	8
DOIs	https://doi.org/10.1021/ic00228a037
State	Published - 1986

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Combined He I/He II Photoelectron Spectroscopic and Hartree-Fock-Slater Investigation of Electronic Structure and Bonding in Uranium Hexamethoxide",

abstract = "The electronic structure of the uranium(VI) alkoxide U(OCH3)6 has been investigated by using a combination of He I/He II photoelectron spectroscopy and discrete variational (DV) Xa molecular orbital calculations. Good agreement is obtained between the experimental and calculated ionization energies. It is found that the low ionization energy features of the photoelectron spectra are due to varying degrees of donation of the oxygen lone pairs to the empty orbitals on the uranium atom and to the reduction of the molecular symmetry to Civia bending of the U-O-C linkages. The methyl groups act as both α and π donors to the oxygen 2p orbitals, increasing the overall donor strength of the alkoxide ligands.",

author = "Bursten, {B. E.} and M. Casarin and Ellis, {D. E.} and I. Fragala and Marks, {T. J.}",

year = "1986",

doi = "10.1021/ic00228a037",

language = "English (US)",

volume = "25",

pages = "1257--1261",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Combined He I/He II Photoelectron Spectroscopic and Hartree-Fock-Slater Investigation of Electronic Structure and Bonding in Uranium Hexamethoxide

AU - Bursten, B. E.

AU - Casarin, M.

AU - Ellis, D. E.

AU - Fragala, I.

AU - Marks, T. J.

PY - 1986

Y1 - 1986

N2 - The electronic structure of the uranium(VI) alkoxide U(OCH3)6 has been investigated by using a combination of He I/He II photoelectron spectroscopy and discrete variational (DV) Xa molecular orbital calculations. Good agreement is obtained between the experimental and calculated ionization energies. It is found that the low ionization energy features of the photoelectron spectra are due to varying degrees of donation of the oxygen lone pairs to the empty orbitals on the uranium atom and to the reduction of the molecular symmetry to Civia bending of the U-O-C linkages. The methyl groups act as both α and π donors to the oxygen 2p orbitals, increasing the overall donor strength of the alkoxide ligands.

AB - The electronic structure of the uranium(VI) alkoxide U(OCH3)6 has been investigated by using a combination of He I/He II photoelectron spectroscopy and discrete variational (DV) Xa molecular orbital calculations. Good agreement is obtained between the experimental and calculated ionization energies. It is found that the low ionization energy features of the photoelectron spectra are due to varying degrees of donation of the oxygen lone pairs to the empty orbitals on the uranium atom and to the reduction of the molecular symmetry to Civia bending of the U-O-C linkages. The methyl groups act as both α and π donors to the oxygen 2p orbitals, increasing the overall donor strength of the alkoxide ligands.

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JO - Inorganic chemistry

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IS - 8

ER -

Combined He I/He II Photoelectron Spectroscopic and Hartree-Fock-Slater Investigation of Electronic Structure and Bonding in Uranium Hexamethoxide

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