Vibrational Properties of the Isotopomers of the Water Dimer Derived from Experiment and Computations

Vibrational Properties of the Isotopomers of the Water Dimer Derived from Experiment and... The water dimer and its 11 deuterated isotopomers are investigated utilizing coupled cluster theory and experimental data as input for a perturbational determination of the isotopomer frequencies. Deuterium substitution reduces the H-bond stretching frequency by maximally 12cm1 from 143 to 131cm1, which makes a spectroscopic differentiation of H- and D-bonds difficult. However, utilizing the 132 frequencies obtained in this work, the identification of all isotopomers is straightforward. The CCSD(T)/CBS value of the binding energy De is 5.00kcalmol1. The binding energy D0 of the water dimer increases upon deuterium substitution from 3.28 to maximally 3.71kcalmol1 reflecting a decrease in the zero point energy contribution. The entropy values of the D-isotopomers increase from 73 to 77 entropy units in line with the general observation that a mass increase leads to larger entropies. All 12 isotopomers possess positive free binding energies at 80K and a reduced pressure of 110Pa, which means that they can be spectroscopically observed under these conditions. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Australian Journal of Chemistry CSIRO Publishing

Vibrational Properties of the Isotopomers of the Water Dimer Derived from Experiment and Computations

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Publisher
CSIRO Publishing
Copyright
Copyright © American Meteorological Society
ISSN
0004-9425
eISSN
1445-0038
D.O.I.
10.1071/CH13479
Publisher site
See Article on Publisher Site

Abstract

The water dimer and its 11 deuterated isotopomers are investigated utilizing coupled cluster theory and experimental data as input for a perturbational determination of the isotopomer frequencies. Deuterium substitution reduces the H-bond stretching frequency by maximally 12cm1 from 143 to 131cm1, which makes a spectroscopic differentiation of H- and D-bonds difficult. However, utilizing the 132 frequencies obtained in this work, the identification of all isotopomers is straightforward. The CCSD(T)/CBS value of the binding energy De is 5.00kcalmol1. The binding energy D0 of the water dimer increases upon deuterium substitution from 3.28 to maximally 3.71kcalmol1 reflecting a decrease in the zero point energy contribution. The entropy values of the D-isotopomers increase from 73 to 77 entropy units in line with the general observation that a mass increase leads to larger entropies. All 12 isotopomers possess positive free binding energies at 80K and a reduced pressure of 110Pa, which means that they can be spectroscopically observed under these conditions.

Journal

Australian Journal of ChemistryCSIRO Publishing

Published: Nov 26, 2013

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