The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: a physical picture

Kasper Mackeprang; Henrik Grum Kjærgaard; Teemu Salmi; Vesa Hänninen; Lauri Halonen

doi:10.1063/1.4873420

The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: a physical picture

Kasper Mackeprang, Henrik Grum Kjærgaard, Teemu Salmi, Vesa Hänninen, Lauri Halonen

Department of Chemistry

35 Citations (Scopus)

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.

Original language	English
Article number	184309
Journal	Journal of Chemical Physics
Volume	140
Number of pages	9
ISSN	0021-9606
DOIs	https://doi.org/10.1063/1.4873420
Publication status	Published - 7 May 2014

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title = "The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: a physical picture",

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.",

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T1 - The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes

T2 - a physical picture

AU - Mackeprang, Kasper

AU - Kjærgaard, Henrik Grum

AU - Salmi, Teemu

AU - Hänninen, Vesa

AU - Halonen, Lauri

PY - 2014/5/7

Y1 - 2014/5/7

N2 - 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.

AB - 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.

U2 - 10.1063/1.4873420

DO - 10.1063/1.4873420

M3 - Journal article

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VL - 140

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

M1 - 184309

ER -

The effect of large amplitude motions on the transition frequency redshift in hydrogen bonded complexes: a physical picture

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