Journal
AUSTRALIAN JOURNAL OF CHEMISTRY
Volume 67, Issue 3, Pages 426-434Publisher
CSIRO PUBLISHING
DOI: 10.1071/CH13479
Keywords
-
Categories
Funding
- National Science Foundation [CHE 1152357]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1152357] Funding Source: National Science Foundation
Ask authors/readers for more resources
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 12 cm(-1) from 143 to 131 cm(-1), 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 D-e is 5.00 kcal mol(-1). The binding energy D-0 of the water dimer increases upon deuterium substitution from 3.28 to maximally 3.71 kcal mol(-1) 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 80 K and a reduced pressure of 110 Pa, which means that they can be spectroscopically observed under these conditions.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available