Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Nee, M.J., Osterwalder, A., Neumark, D.M., Kaposta, C., Uhalte, C.C., Xie, T., Kaledin, A., Bowman, J.M., Carter, S. and Asmis, K.R. (2004) Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-. Journal of Chemical Physics, 121 (15). pp. 7259-7268. ISSN 0021-9606 doi: 10.1063/1.1794671

Abstract/Summary

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 mum (590-1666 cm-1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. (C) 2004 American Institute of Physics.