title: High resolution infrared spectra of a carbon dioxide molecule solvated with helium atoms.
abstract: Infrared spectra of He(N)-CO(2) clusters with N up to about 20 have been studied in the region of the CO(2) nu(3) fundamental band ( approximately 2350 cm(-1)) using a tunable diode laser spectrometer and pulsed supersonic jet source with cooled (>-150 degrees C) pinhole or slit nozzles and high backing pressures (<40 atm). Compared to previous studies of He(N)-OCS and -N(2)O clusters, the higher symmetry of CO(2) results in simpler spectra but less information content. Discrete rotation-vibration transitions have been assigned for N=3-17, and their analysis yields the variation of the vibrational band origin and B rotational constant over this size range. The band origin variation is similar to He(N)-OCS, with an initial blueshift up to N=5, followed by a monotonic redshift, consistent with a model where the first five He atoms fill a ring around the equator of the molecule, forcing subsequent He atom density to locate closer to the ends. The B value initially drops as expected for a normal molecule, reaching a minimum for N=5. Its subsequent rise for N=6 to 11 can be interpreted as the transition from a normal (though floppy) molecule to a quantum solvation regime, where the CO(2) molecule starts to rotate separately from the He atoms. For N>13, the B value becomes approximately constant with a value about 17% larger than that measured in much larger helium nanodroplets.
authors.affiliation: Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.
authors.forename: Jian
authors.initials: J
authors.lastname: Tang
authors.forename: A R W
authors.initials: AR
authors.lastname: McKellar