Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

V + ( H 2 O ) Ar n and V+(D2O)Arn complexes are studied with mass-selected infrared photodissociation spectroscopy in the O–H (O–D) stretch region. Two vibrational bands are measured 50–80 cm−1 to the red from the symmetric and asymmetric stretches in free water. Rotational analysis for V+(H2O)Ar indicates a C2v geometry with argon opposite water and significant expansion of the H–O–H angle. The v=1 level in the asymmetric stretch undergoes distortion consistent with selective excitation into the coordinate of an insertion reaction.