Toward Understanding Mobile Proton Behavior from First Principles Calculation:  The Short Hydrogen Bond in Crystalline Urea−Phosphoric Acid

The dynamics of the intermolecular short hydrogen bond in the molecular complex of urea and phosphoric acid are investigated using plane-wave density functional theory. Results indicate migration of the proton toward the center of the hydrogen bond as temperature is increased, in line with recent ex...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-03, Vol.127 (11), p.4042-4048
Main Authors: Morrison, Carole A, Siddick, Muhammad M, Camp, Philip J, Wilson, Chick C
Format: Article
Language:English
Subjects:
Condensed matter: structure, mechanical and thermal properties
Crystal binding
cohesive energy
Crystalline state (including molecular motions in solids)
Exact sciences and technology
Physics
Structure of solids and liquids
crystallography
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Summary:The dynamics of the intermolecular short hydrogen bond in the molecular complex of urea and phosphoric acid are investigated using plane-wave density functional theory. Results indicate migration of the proton toward the center of the hydrogen bond as temperature is increased, in line with recent experimental measurements. Computed vibrational frequencies show favorable agreement with experimental measurement. An analysis of existing neutron diffraction data leads us to conclude that the effective potential well experienced by the proton is temperature-dependent. Inspired by our computations and theoretical analysis, we offer a possible explanation for the proton migration phenomenon.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja043327z