101. The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: A physical picture.
- Author
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Mackeprang, Kasper, Kjaergaard, Henrik G., Salmi, Teemu, Hänninen, Vesa, and Halonen, Lauri
- Subjects
SCATTERING amplitude (Physics) ,REDSHIFT ,HYDROGEN ,COMPLEX compounds ,VIBRATIONAL transitions (Molecular physics) ,QUANTUM chromodynamics ,WAVENUMBER ,DIMERS - Abstract
We describe the vibrational transitions of the donor unit in water dimer with an approach that is based on a three-dimensional local mode model.We perform a perturbative treatment of the intermolecular vibrational modes to improve the transition wavenumber of the hydrogen bonded OH-stretching transition. The model accurately predicts the transition wavenumbers of the vibrations in water dimer compared to experimental values and provides a physical picture that explains the redshift of the hydrogen bonded OH-oscillator.We find that it is unnecessary to include all six intermolecular modes in the vibrational model and that their effect can, to a good approximation, be computed using a potential energy surface calculated at a lower level electronic structure method than that used for the unperturbed model. [ABSTRACT FROM AUTHOR]
- Published
- 2014
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