title: Rotationally resolved infrared spectrum of the Na(+)-D2 complex: an experimental and theoretical study.
abstract: The infrared spectrum of mass-selected Na(+)-D(2) complexes is recorded in the D-D stretch vibration region (2915-2972 cm(-1)) by detecting Na(+) photofragments resulting from photo-excitation of the complexes. Analysis of the rotationally resolved spectrum confirms a T-shaped equilibrium geometry for the complex and a vibrationally averaged intermolecular bond length of 2.461 Å. The D-D stretch band centre occurs at 2944.04 cm(-1), representing a -49.6 cm(-1) shift from the Q(1)(0) transition of the free D(2) molecule. Variational rovibrational energy level calculations are performed for Na(+)-D(2) utilising an ab initio potential energy surface developed previously for investigating the Na(+)-H(2) complex [B. L. J. Poad et al., J. Chem. Phys. 129, 184306 (2008)]. The theoretical approach predicts a dissociation energy for Na(+)-D(2) of 923 cm(-1) with respect to the Na(+)+ D(2) limit, reproduces the experimental rotational constants to within 1-2%, and gives a simulated spectrum closely matching the experimental infrared spectrum.
authors.affiliation: School of Chemistry, University of Melbourne, Parkville, Victoria 3010, Australia.
authors.forename: B L J
authors.initials: BL
authors.lastname: Poad
authors.forename: V
authors.initials: V
authors.lastname: Dryza
authors.forename: J
authors.initials: J
authors.lastname: Kłos
authors.forename: A A
authors.initials: AA
authors.lastname: Buchachenko
authors.forename: E J
authors.initials: EJ
authors.lastname: Bieske