Publication Details

Poad, B. L., Dryza, V., Klos, J., Buchachenko, A. A. & Bieske, E. J. (2011). Rotationally resolved infrared spectrum of the Na+-D2 complex: an experimental and theoretical study. Journal of Chemical Physics, 134 (21), 214302-1-214302-6.


The infrared spectrum of mass-selected Na+-D2 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 Q1(0) transition of the free D2 molecule. Variational rovibrational energy level calculations are performed for Na+-D2 utilising an ab initio potential energy surface developed previously for investigating the Na+-H2 complex [B. L. J. Poad et al., J. Chem. Phys. 129, 184306 (2008)]10.1063/1.3005785. The theoretical approach predicts a dissociation energy for Na+-D2 of 923 cm−1 with respect to the Na++ D2 limit, reproduces the experimental rotational constants to within 1-2%, and gives a simulated spectrum closely matching the experimental infrared spectrum.



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