The bond dissociation energy of VO measured by resonant three-photon ionization spectroscopy

The predissociation threshold of VO has been measured using resonant three-photon ionization (R3PI) spectroscopy. Given the high density of electronic states in the molecule, it is argued that the molecule dissociates rapidly as soon as the thermochemical bond dissociation energy (BDE) is exceeded, allowing the measured predissociation threshold to be assigned as the BDE. This is the first time a BDE has been measured using the R3PI method. The first photon is provided by an optical parametric oscillator (OPO) laser that promotes VO into a high-energy, discrete vibronic state. A tunable dye laser then excites the molecule further to a resonant state close to the dissociation limit where there is a quasi-continuum of states. A second photon from the same dye laser pulse ionizes the molecule, generating VO⁺ ions. The dye laser is then scanned to higher energies, and when the energy of one OPO photon plus one dye photon exceeds the BDE, the molecule dissociates before another dye photon can be absorbed to induce ionization. The combined photon energy at the sharp drop in the ion signal is assigned as the BDE. The experiment has been repeated using four different intermediate states, all yielding the same BDE, D₀(VO) = 6.545(2) eV. Using thermochemical cycles, a revised value for the BDE of cationic VO is obtained, D₀(V⁺-O) = 6.053(2) eV. The 0 K enthalpy of formation for VO(g) is also derived as Δ_fH_0K ⁰VO(g) = 128.6(1.0) kJ mol^-1. Previous spectroscopic and thermochemical studies of VO are reviewed.