Communication: A vibrational study of titanium dioxide cation using the vacuum ultraviolet laser pulsed field ionization-photoelectron method

Abstract

We have successfully measured the vacuum ultraviolet (VUV) laser photoionization efficiency and pulsed field ionization-photoelectron (PFI-PE) spectra of cold titanium dioxide (TiO(2)) prepared by a supersonically cooled laser ablation source. The VUV-PFI-PE spectrum thus obtained exhibits long progressions of the v(2)(+)(a(1)) bending and the combination of v(1)(+)(a(1)) stretching and v(2)(+)(a(1)) bending vibrational modes of the TiO(2)(+)(X(2)B(2)) ion. The pattern of Franck-Condon factors observed indicates that the O-Ti-O bond angle of the TiO(2)(+)(X(2)B(2)) ion is significantly different from that of the TiO(2)(X(1)A(1)) neutral, whereas the change of the Ti-O bond distance is very minor upon the photoionization transition. The analysis of the PFI-PE bands has made possible the determination of the adiabatic ionization energy for TiO(2), IE(TiO(2)) = 77215.9 ± 1.2 cm(-1) (9.57355 ± 0.00015 eV), the harmonic vibrational frequencies, ω(1)(+) = 829.1 ± 2.0 cm(-1) and ω(2)(+) = 248.7 ± 0.6 cm(-1), and the anharmonic coefficients, χ(11)(+) = 5.57 ± 0.65 cm(-1), χ(22)(+) = 0.08 ± 0.06 cm(-1), and χ(12)(+) = -4.51 ± 0.30 cm(-1) for the TiO(2)(+)(X(2)B(2)) ground state.