Electronic and vibrational spectroscopy and vibrationally mediated photodissociation of V+(OCO)

Electronic spectra of gas-phase V+(OCO) are measured in the near-infrared from 6050 to 7420 cm(-1) and in the visible from 15,500 to 16,560 cm(-1), using photofragment spectroscopy. The near-IR band is complex, with a 107 cm(-1) progression in the metal-ligand stretch. The visible band shows clearly resolved vibrational progressions in the metal-ligand stretch and rock, and in the OCO bend, as observed by Brucat and co-workers. A vibrational hot band gives the metal-ligand stretch frequency in the ground electronic state nu3' = 210 cm(-1). The OCO antisymmetric stretch frequency in the ground electronic state (nu1') is measured by using vibrationally mediated photodissociation. An IR laser vibrationally excites ions to nu1' = 1. Vibrationally excited ions selectively dissociate following absorption of a second, visible photon at the nu1' = 1 <-- nu1' = 1 transition. Rotational structure in the resulting vibrational action spectrum confirms that V+(OCO) is linear and gives nu1' = 2392.0 cm(-1). The OCO antisymmetric stretch frequency in the excited electronic state is nu1' = 2368 cm(-1). Both show a blue shift from the value in free CO2, due to interaction with the metal. Larger blue shifts observed for complexes with fewer ligands agree with trends seen for larger V+(OCO)n clusters.