Infrared spectroscopy of RG-Co+(H2O) complexes (RG = Ar, Ne, He): The role of rare gas "tag" atoms.

Abstract

RGn-Co+(H2O) cation complexes (RG = Ar, Ne, He) are generated in a supersonic expansion by pulsed laser vaporization. Complexes are mass-selected using a time-of-flight spectrometer and studied with infrared laser photodissociation spectroscopy, measuring the respective mass channels corresponding to the elimination of the rare gas "tag" atom. Spectral patterns and theory indicate that the structures of the ions with a single rare gas atom have this bound to the cobalt cation opposite the water moiety in a near-C2v arrangement. The O-H stretch vibrations of the complex are shifted compared to those of water because of the metal cation charge-transfer interaction; these frequencies also vary systematically with the rare gas atom attached. The efficiencies of photodissociation also vary with the rare gas atoms because of their widely different binding energies to the cobalt cation. The spectrum of the argon complex could only be measured when at least three argon atoms were attached. In the case of the helium complex, the low binding energy allows the spectra to be measured for the low-frequency H-O-H scissors bending mode and for the O-D stretches of the deuterated analog. The partially resolved rotational structure for the antisymmetric O-H and O-D stretches reveals the temperature of these complexes (6 K) and establishes the electronic ground state. The helium complex has the same 3B1 ground state as the tag-free complex studied previously by Metz and co-workers ["Dissociation energy and electronic and vibrational spectroscopy of Co+(H2O) and its isotopomers," J. Phys. Chem. A 117, 1254 (2013)], but the A rotational constant is contaminated by vibrational averaging from the bending motion of the helium.