Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

Abstract

Ti- and V-bz2 (bz=C6H6) sandwich complexes have been prepared in a laser-ablation cluster beam source and studied by pulsed field ionization-zero electron kinetic energy photoelectron spectroscopy and theoretical calculations. The ground electronic states of the neutral Ti- and V-bz2 complexes are determined to be 1A1g and 2A1g, and their ionization energies are measured to be 5.732+/-0.001 and 5.784+/-0.002 eV, respectively. These neutral complexes have eta6 binding and are in an eclipsed D6h configuration with flat benzene rings. Ionization of the 1A1g and 2A1g neutral states of Ti- and V-bz2 yields the 2B1g and 3B1g ion states, respectively, in a D2h point group with slightly puckered benzene rings. In addition, the binding and structures of these two complexes are compared with other first-row transition metal bis(benzene) sandwiches.

Binding sites, rotational conformers, and electronic states of Sc–C6H5X (X=F, CH3, OH, and CN) probed by pulsed-field-ionization electron spectroscopy

“…The full width at half maximum of this peak is about 12 cm −1 and the broad linewidth is due to unresolved rovibronic transitions. 28,30,31,34 Measurements with a heavy carrier gas would reduce the linewidth by decreasing rotational temperatures of the neutral molecules. Unfortunately, experiments with Ar or Ar/He carriers were unsuccessful due to very weak signals.…”

“…29 The B3LYP ͑Becke's three parameter hybrid functional with the correlation functional of Lee, Yang, and Parr͒ functional was selected because previous studies have shown that this method yielded good agreement with experimental ZEKE spectra of metal-aromatic complexes. 28,30,31 In these calculations, the all electron 6-311+ G͑d , p͒ basis was used for all atoms.…”

Optical to ultraviolet spectra of sandwiches of benzene and transition metal atoms: Time dependent density functional theory and many-body calculations

“…Recently, Sohnlein et al 42 have performed ZEKE-PES measurements on bis-benzene complexes of titanium and vanadium, which provide information on the energetics of the occupied orbitals, but not of the unoccupied ones, and hence they cannot be compared with the optical spectra. On the other hand, Zheng et al 43 have performed anion photoelectron measurements on ͑Ti n Bz m ͒ − .…”

Half sandwich structures of (M=Ag and Au): An experimental and theoretical study

“…Kaya group [5][6][7] systematically studied the properties of 3d transition metal-benzene complexes M m (benzene) n (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni) in the gas phase, including their structures, photodissociation processes, bonding energies and ionization energies. But the reported experimental [12][13][14][15] and theoretical [19,[22][23][24][25][26][27][28][29] studies are mainly on the transition metal-benzene cationic and neutral complexes. However, the experimental and theoretical studies of metal-benzene anion complexes are rarely reported.…”

“…In recent years, many experimental [5][6][7][8][9][10][11][12][13][14][15] and theoretical [16][17][18][19][20][21][22][23][24][25][26][27][28][29] investigations on the interaction of metal clusters with benzene in gas phase were extensively reported. Kaya group [5][6][7] systematically studied the properties of 3d transition metal-benzene complexes M m (benzene) n (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni) in the gas phase, including their structures, photodissociation processes, bonding energies and ionization energies.…”