On the connection between proton transport, structural diffusion, and reorientation of the hydrated hydroxide ion as a function of temperature

Zhonghua Ma, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

The properties of the hydrated hydroxide ion OH-(aq) stand in sharp contrast to those of most other aqueous ions. Chief among these is its anomalously high mobility, which is shared only by the aqueous hydronium ion H3O+(aq). However, while the transport mechanism of H 3O+(aq) is now well understood, the details of OH -(aq) diffusion at ambient conditions are just beginning to emerge, and the effects of temperature on the transport mechanism remain largely unelucidated. Here, we undertake an ab initio molecular dynamics study of the effect of temperature on the solvation and transport of OH-(aq). In addition to revealing new details of the transport process, our analysis provides an explanation for the experimentally observed temperature dependence of the OH-(aq) reorientation time. The calculations reveal a suppression of proton transfer events that underly the structural diffusion process caused by a pronounced change in the population of dominant OH -(aq) solvation complexes.

Original languageEnglish (US)
Pages (from-to)177-182
Number of pages6
JournalChemical Physics Letters
Volume511
Issue number4-6
DOIs
StatePublished - Aug 5 2011

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hydroxides
retraining
solvation
Protons
hydronium ions
protons
ions
Solvation
retarding
molecular dynamics
Temperature
temperature dependence
temperature
Proton transfer
Molecular dynamics
hydroxide ion
Ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

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abstract = "The properties of the hydrated hydroxide ion OH-(aq) stand in sharp contrast to those of most other aqueous ions. Chief among these is its anomalously high mobility, which is shared only by the aqueous hydronium ion H3O+(aq). However, while the transport mechanism of H 3O+(aq) is now well understood, the details of OH -(aq) diffusion at ambient conditions are just beginning to emerge, and the effects of temperature on the transport mechanism remain largely unelucidated. Here, we undertake an ab initio molecular dynamics study of the effect of temperature on the solvation and transport of OH-(aq). In addition to revealing new details of the transport process, our analysis provides an explanation for the experimentally observed temperature dependence of the OH-(aq) reorientation time. The calculations reveal a suppression of proton transfer events that underly the structural diffusion process caused by a pronounced change in the population of dominant OH -(aq) solvation complexes.",
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N2 - The properties of the hydrated hydroxide ion OH-(aq) stand in sharp contrast to those of most other aqueous ions. Chief among these is its anomalously high mobility, which is shared only by the aqueous hydronium ion H3O+(aq). However, while the transport mechanism of H 3O+(aq) is now well understood, the details of OH -(aq) diffusion at ambient conditions are just beginning to emerge, and the effects of temperature on the transport mechanism remain largely unelucidated. Here, we undertake an ab initio molecular dynamics study of the effect of temperature on the solvation and transport of OH-(aq). In addition to revealing new details of the transport process, our analysis provides an explanation for the experimentally observed temperature dependence of the OH-(aq) reorientation time. The calculations reveal a suppression of proton transfer events that underly the structural diffusion process caused by a pronounced change in the population of dominant OH -(aq) solvation complexes.

AB - The properties of the hydrated hydroxide ion OH-(aq) stand in sharp contrast to those of most other aqueous ions. Chief among these is its anomalously high mobility, which is shared only by the aqueous hydronium ion H3O+(aq). However, while the transport mechanism of H 3O+(aq) is now well understood, the details of OH -(aq) diffusion at ambient conditions are just beginning to emerge, and the effects of temperature on the transport mechanism remain largely unelucidated. Here, we undertake an ab initio molecular dynamics study of the effect of temperature on the solvation and transport of OH-(aq). In addition to revealing new details of the transport process, our analysis provides an explanation for the experimentally observed temperature dependence of the OH-(aq) reorientation time. The calculations reveal a suppression of proton transfer events that underly the structural diffusion process caused by a pronounced change in the population of dominant OH -(aq) solvation complexes.

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