Gas phase high temperature photoelectron spectroscopy: an investigation of the transition metals scandium and vanadium

The He(I) photoelectron spectra of atomic scandium and vanadium have been recorded in the gas-phase. For scandium two bands associated with a (4s)^?1 ionization and one band associated with a (3d)^?1 ionization of the neutral atom have been observed. Measurement of their relative intensities allows the σ_3d:σ_4s photoionization cross-section ratio in atomic scandium to be estimated as 57.1 ± 9.0. In the atomic vanadium spectrum, six bands were seen. Four of these correspond to (3d)^?1 and (4s)^?1 ionizations of the ground state of the neutral atom, the V a⁴F state, whereas two bands correspond to (3d)^?1 ionizations of an excited state, the V a₆D state, which is approximately 2100 cm^?1 above the ground state. Measurement of the intensities of bands arising from the V a₄F state allows σ_3d:σ_4s to be estimated as 29.8 ± 2.5 for vanadium. Spectra of vanadium have been recorded with both single- and multi-detector photoelectron spectrometers. Comparison of the data acquisition rates obtained with both spectrometers demonstrates the advantage of using a multidetector instrument in high temperature photoelectron spectroscopy.