Effect of quantum nuclear motion on hydrogen bonding

McKenzie, Ross H., Bekker, Christiaan, Athokpam, Bijyalaxmi and Ramesh, Sai G. (2014) Effect of quantum nuclear motion on hydrogen bonding. Journal of Chemical Physics, 140 17: 174508-174508-13. doi:10.1063/1.4873352

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Author McKenzie, Ross H.
Bekker, Christiaan
Athokpam, Bijyalaxmi
Ramesh, Sai G.
Title Effect of quantum nuclear motion on hydrogen bonding
Journal name Journal of Chemical Physics   Check publisher's open access policy
ISSN 0021-9606
Publication date 2014-05-07
Year available 2014
Sub-type Article (original research)
DOI 10.1063/1.4873352
Open Access Status File (Publisher version)
Volume 140
Issue 17
Start page 174508
End page 174508-13
Total pages 13
Place of publication College Park, MD United States
Publisher American Institute of Physics
Language eng
Subject 3100 Physics and Astronomy
1606 Political Science
Abstract This work considers how the properties of hydrogen bonded complexes, X-H Y, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (X) and acceptor (Y) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-HO complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4 - 3.0 Å, i.e., from strong to weak hydrogen bonds. The position of the proton (which determines the X-H bond length) and its longitudinal vibrational frequency, along with the isotope effects in both are described quantitatively. An analysis of the secondary geometric isotope effect, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of bending modes is also considered: their quantum effects compete with those of the stretching mode for weak to moderate H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several trends.
Keyword Hamiltonian cycle
Q-Index Code C1
Q-Index Status Confirmed Code
Grant ID DP0877875
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Mathematics and Physics
Official 2015 Collection
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Citation counts: TR Web of Science Citation Count  Cited 26 times in Thomson Reuters Web of Science Article | Citations
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