Density functional theory Perdew–Burke–Ernzerhof [Perdew et al., Phys. Rev. Lett. 77, 3865 (1996)] molecular dynamics simulations of aqueous solutions of orthophosphate species provide new insights into hydrogen transfer and intermolecular and hydration properties of these important aqueous species. Extensive Car–Parrinello molecular dynamics simulations of the orthophosphate ion , of the hydrogen phosphate anions, and , and of the orthophosphoric acid, , in explicit water show that the process of proton transfer from to the surrounding water molecules is very fast, less than 1 ps, and indicate that the dehydrogenation occurs through a concerted proton hopping mechanism, which involves and three water molecules. Analysis of the intermolecular -water structure shows that the anions have a significant effect on the H-bonding network of bulk water and the presence of moieties induce the formation of new types of H–H interactions around this orthophosphate. Calculated probability distributions of the coordination numbers of the first hydration shell of , , and show that these phosphate species display a flexible first coordination shell (between 7 and 13 water molecules) and that the flexibility increases on going from to . The strength and number of hydrogen bonds of , , and are determined through a detailed analysis of the structural correlation functions. In particular, the H-bond interactions between the oxygen atoms of the phosphates and the surrounding water molecules, which decrease on going from to the hydrogenated species, explain the diminished effect on the structure of water with the increasing hydrogenation of the orthophosphate anions.
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21 June 2009
Research Article|
June 15 2009
Hydrogen transfer and hydration properties of in water studied by first principles molecular dynamics simulations
Emilia Tang;
Emilia Tang
Department of Chemistry, Christopher Ingold Laboratories,
University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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Devis Di Tommaso;
Devis Di Tommaso
a)
Department of Chemistry, Christopher Ingold Laboratories,
University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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Nora H. de Leeuw
Nora H. de Leeuw
a)
Department of Chemistry, Christopher Ingold Laboratories,
University College London
, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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a)
Authors to whom correspondence should be addressed. Electronic addresses: uccaddi@ucl.ac.uk and n.h.deleeuw@ucl.ac.uk.
J. Chem. Phys. 130, 234502 (2009)
Article history
Received:
March 26 2009
Accepted:
May 07 2009
Citation
Emilia Tang, Devis Di Tommaso, Nora H. de Leeuw; Hydrogen transfer and hydration properties of in water studied by first principles molecular dynamics simulations. J. Chem. Phys. 21 June 2009; 130 (23): 234502. https://doi.org/10.1063/1.3143952
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