Variable photon energy photoelectron spectroscopic and theoretical investigations of the electronic structure of TiCl{sub 4}

Journal Article · Wed Oct 26 04:00:00 EDT 1994 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00100a038· OSTI ID:420982

Bursten, B E ^[1]; Green, J C; Sze, K H ^[2]

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1. Ohio State Univ., Columbus, OH (United States)
2. Univ. of Oxford (United Kingdom); and others

The photoelectron spectrum of TiCl{sub 4} has been measured using synchrotron radiation over the incident photon energy range 17-69 eV, and relative partial photoionization cross sections have been derived for the valence bands. Band A (1t{sub 1}{sup {minus}1}) and band B (3t{sub 2}{sup {minus}1}) display cross section variations typical of Cl 3p atomic orbital-localized levels. Bands C+D show cross section enhancement between 40 and 60 eV and are assigned to le{sup {minus}1} and 2t{sub 2}{sup {minus}1}. B and E (2a{sub 1}{sup {minus}1}) shows no such feature and has cross section behavior which is appreciably different from that of any of the other bands. The small cross section maximum at 40 eV is attributed to a molecular shape resonance. Discrete variational X{alpha} calculations support this orbital ordering, and quantitative agreement is found between the experimental and calculated ionization energies. Photoionization cross sections were calculated using the multiple-scattering X{alpha} method. Good agreement was found between experimental and theoretical branching ratios, confirming the assignment and suggesting that the resonances found in the 2t{sub 2} and 2a{sub 1} orbital cross sections are due to multiple scattering from the localized Cl electrons. The minimum in the 3t{sub 2} cross section is associated with the Cooper minimum of the Cl 3p orbital.

• Sponsoring Organization: USDOE
• DOE Contract Number: FG02-86ER13529
• OSTI ID: 420982
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 22 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ELECTRONIC STRUCTURE
MATHEMATICAL MODELS
PHOTOELECTRON SPECTROSCOPY
SYNCHROTRON RADIATION
TITANIUM CHLORIDES