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Article
Properties of the B+-H2 and B+-D2 complexes: a theoretical and spectroscopic study
Faculty of Science - Papers (Archive)
  • B L. J Poad, University of Wollongong
  • V Dryza, University of Melbourne
  • A A Buchachenko, Moscow State University
  • J Kos, University of Maryland
  • E J Bieske, University of Melbourne
RIS ID
68230
Publication Date
1-1-2012
Publication Details

Poad, B. L. J., Dryza, V., Buchachenko, A. A., Kos, J. & Bieske, E. J. (2012). Properties of the B+-H2 and B+-D2 complexes: a theoretical and spectroscopic study. Journal of Chemical Physics, 137 (12), 124312-1-124312-8.

Abstract
The rotationally resolved infrared spectrum of the B+-D2 ion-neutral complex is recorded in the D-D stretch vibration region (2805–2875  cm−1) by detecting B+ photofragments. Analysis of the spectrum confirms a T-shaped equilibrium geometry for the B+-D2 complex with a vibrationally averaged intermolecular bond length of 2.247 Å, around 0.02 Å shorter than for the previously characterised B+-H2 complex [V. Dryza, B. L. J. Poad, and E. J. Bieske, J. Am. Chem. Soc. 130, 12986 (2008)10.1021/ja8018302]. The D-D stretch band centre occurs at 2839.76 ± 0.10 cm−1, representing a −153.8  cm−1 shift from the Q1(0) transition of the free D2 molecule. A new three dimensional ab initio potential energy surface for the B++H2 interaction is calculated using the coupled cluster RCCSD(T) method and is used in variational calculations for the rovibrational energies of B+-H2 and B+-D2. The calculations predict dissociation energies of 1254  cm−1 for B+-H2 with respect to the B++H2 (j = 0) limit, and 1313  cm−1 for B+-D2 with respect to the B++D2 (j = 0) limit. The theoretical approach reproduces the rotational and centrifugal constants of the B+-H2 and B+-D2 complexes to within 3%, and the magnitude of the contraction of the intermolecular bond accompanying excitation of the H2 or D2 sub-unit, but underestimates the H-H and D-D vibrational band shifts by 7%–8%. Combining the theoretical and experimental results allows a new, more accurate estimation for the B+-H2 band origin (3939.64 ± 0.10  cm−1).
Citation Information
B L. J Poad, V Dryza, A A Buchachenko, J Kos, et al.. "Properties of the B+-H2 and B+-D2 complexes: a theoretical and spectroscopic study" (2012)
Available at: http://works.bepress.com/berwyck_poad/7/