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DOI: 10.1039/A605753E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 213-220

Investigation of the bonding in methyl titanium trichloride by variable-energy photoelectron spectroscopy and density functional calculations[hair space]

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Christian N. Field, Jennifer C. Green, Nikolas Kaltsoyannis, G. Sean McGrady, Aidan N. Moody, Michele Siggel and Monica De Simone

Abstract

Preparation of an authentically pure sample of [TiMeCl3] has enabled measurement of its photoelectron spectrum with photon energies varying between 20 and 50 eV. Study of the relative partial photoionisation cross-sections of the valence photoelectron bands has enabled a full assignment of the related ion states. The character of the ionising orbitals was also deduced from the cross-section variations. The titanium–carbon bond was shown to have a significant Ti 3d character. Density functional calculations at the non-local level, including estimates of the ionisation energies using Slater’s transition-state method, are in good agreement as to the ion state ordering. Fragment analysis of the one-electron eigenfunctions is fully consistent with the experimentally deduced orbital character.

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