title: Molecular geometry of vanadium dichloride and vanadium trichloride: a gas-phase electron diffraction and computational study.
abstract: The molecular geometries of VCl2 and VCl3 have been determined by computations and gas-phase electron diffraction (ED). The ED study is a reinvestigation of the previously published analysis for VCl2. The structure of the vanadium dichloride dimer has also been calculated. According to our joint ED and computational study, the evaporation of a solid sample of VCl2 resulted in about 66% vanadium trichloride and 34% vanadium dichloride in the vapor. Vanadium dichloride is unambiguously linear in its 4Sigma(g)+ ground electronic state. For VCl3, all computations yielded a Jahn-Teller-distorted ground-state structure of C(2v) symmetry. However, it lies merely less than 3 kJ/mol lower than the 3E'' state (D(3h) symmetry). Due to the dynamic nature of the Jahn-Teller effect in this case, rigorous distinction cannot be made between the planar models of either D(3h) symmetry or C(2v) symmetry for the equilibrium structure of VCl3. Furthermore, the presence of several low-lying excited electronic states of VCl3 is expected in the high-temperature vapor. To our knowledge, this is the first experimental and computational study of the VCl3 molecule.
authors.affiliation: Materials Structure and Modeling Research Group of the Hungarian Academy of Sciences, Budapest University of Technology and Economics, P.O. Box 91, 1521 Budapest, Hungary.
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Varga
authors.forename: Brian
authors.initials: B
authors.lastname: Vest
authors.forename: Peter
authors.initials: P
authors.lastname: Schwerdtfeger
authors.forename: Magdolna
authors.initials: M
authors.lastname: Hargittai