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.
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14 May 2014
Research Article|
May 09 2014
The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: A physical picture
Kasper Mackeprang;
Kasper Mackeprang
1Department of Chemistry,
University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
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Henrik G. Kjaergaard;
Henrik G. Kjaergaard
a)
1Department of Chemistry,
University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
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Teemu Salmi;
Teemu Salmi
2Laboratory of Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014,
University of Helsinki
, Helsinki, Finland
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Vesa Hänninen;
Vesa Hänninen
2Laboratory of Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014,
University of Helsinki
, Helsinki, Finland
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Lauri Halonen
Lauri Halonen
b)
2Laboratory of Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014,
University of Helsinki
, Helsinki, Finland
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a)
Electronic mail: hgk@chem.ku.dk
b)
Electronic mail: lauri.halonen@helsinki.fi
J. Chem. Phys. 140, 184309 (2014)
Article history
Received:
February 20 2014
Accepted:
April 15 2014
Citation
Kasper Mackeprang, Henrik G. Kjaergaard, Teemu Salmi, Vesa Hänninen, Lauri Halonen; The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: A physical picture. J. Chem. Phys. 14 May 2014; 140 (18): 184309. https://doi.org/10.1063/1.4873420
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