skip to main content

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

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.
Authors:
;  [1] ; ; ;  [2]
  1. Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø (Denmark)
  2. Laboratory of Physical Chemistry, Department of Chemistry, P.O. Box 55, A.I. Virtasen aukio 1, FI-00014, University of Helsinki, Helsinki (Finland)
Publication Date:
OSTI Identifier:
22252883
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRONIC STRUCTURE; HYDROGEN; OSCILLATORS; POTENTIAL ENERGY; RED SHIFT; SURFACES; WATER