Resonant two photon ionization spectroscopy of the molecules V2, VNb, and Nb2

Abstract

Resonant two photon ionization (R2PI) spectroscopy was used to obtain detailed spectroscopic information on the neutral and cation ground states of the jet-cooled molecules V2, VNb, and Nb2. By recording photoionization efficiency (PIE) spectra, their adiabatic ionization potentials were determined to be 51 269(5) cm−1 (V2), 51 554(10) cm−1 (VNb), and 51 359(10) cm−1 (Nb2). In VNb, we used different ionization routes to determine that the splitting between the Ω=0 and Ω=1 spin–orbit components of the X 3Σ− ground state was 230(3) cm−1. In the case of V2 and VNb, two thresholds were observed in the PIE spectra recorded via Ω=1 intermediate states. We were thus able to assign the ground states of V+2 and VNb+ as having 4Σ− symmetry, with second-order spin–orbit splittings of 20(3) and 82(3) cm−1, respectively. A simple model was applied to calculate the locations of the 1Σ+ and 2Σ+ states which are responsible for the second-order spin–orbit splitting of the neutral and cation ground states, respectively. One-color R2PI spectroscopy was employed to determine the bond dissociation energy of VNb, the result D00=30 562(10) cm−1 being obtained. The implications of our measurements regarding the relative bond strengths of the neutral and cationic dimers are discussed.