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

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.