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How phonons govern the Behavior of short, strong hydrogen bonds in urea-phosphoric acid

Fontaine-Vive, F.; Johnson, M.R.; Kearley, G.J.; Howard, J.A.K.; Parker, S.F.

Authors

F. Fontaine-Vive

M.R. Johnson

G.J. Kearley

J.A.K. Howard

S.F. Parker



Abstract

Recent neutron diffraction data have shown that the hydrogen atom involved in the short, strong hydrogen bond in urea-phosphoric acid migrates toward the midpoint of the hydrogen bond as the temperature increases. With the help of solid state ab initio calculations and inelastic neutron scattering, we have investigated the temperature dependence of the structural and vibrational properties of the system. The potential energy surface of the proton in the short, strong hydrogen bond and the thermal population of the energy levels therein cannot account for the observed proton migration. Ab initio molecular dynamics simulations clearly reveal the migration of the proton. This molecular dynamics result was reported recently by other authors, but they only offered a tentative explanation in terms of a resonance between high-frequency vibrations, which is not supported by the calculations presented here. We explain the proton migration in terms of phonon-driven structural fluctuations and their impact on the temperature-dependent evolution of the potential energy surface of the short hydrogen-bond proton.

Citation

Fontaine-Vive, F., Johnson, M., Kearley, G., Howard, J., & Parker, S. (2006). How phonons govern the Behavior of short, strong hydrogen bonds in urea-phosphoric acid. Journal of the American Chemical Society, 128(9), 2963-2969. https://doi.org/10.1021/ja0569712

Journal Article Type Article
Publication Date Mar 1, 2006
Deposit Date Jan 23, 2008
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 128
Issue 9
Pages 2963-2969
DOI https://doi.org/10.1021/ja0569712