Ab initio molecular dynamics simulation of the solvation and transport of H3O+ and OH- ions in water

Mark Tuckerman, Kari Laasonen, Michiel Sprik, Michele Parrinello

Research output: Contribution to journalArticle

Abstract

Applying the ab initio molecular dynamics method, we have studied the solvation and dynamics of an excess proton and a proton hole in liquid water. We find for the H3O+ ion a dynamic solvation complex which continuously fluctuates between a (H5O2)+ and (H9O4)+ structure as a result of proton transfer. The results of the simulation strongly suggest that the rate-limiting step for the migration of the excess proton is the concerted dynamics of the second solvation shell hydrogen bonded to the ligand H2O molecules. The OH- ion has a predominantly planar 4-fold coordination. Proton transfer is only observed when this (H9O5)- complex is transformed into a tetrahedral (H7O4)- configuration. The formation of this more open complex determines the OH- diffusion rate.

Original languageEnglish (US)
Pages (from-to)5749-5752
Number of pages4
JournalJournal of Physical Chemistry
Volume99
Issue number16
StatePublished - 1995

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Solvation
solvation
Molecular dynamics
Protons
Proton transfer
Ions
molecular dynamics
protons
Water
Computer simulation
water
ions
simulation
Hydrogen
Ligands
Molecules
Liquids
hydroxide ion
ligands
hydrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ab initio molecular dynamics simulation of the solvation and transport of H3O+ and OH- ions in water. / Tuckerman, Mark; Laasonen, Kari; Sprik, Michiel; Parrinello, Michele.

In: Journal of Physical Chemistry, Vol. 99, No. 16, 1995, p. 5749-5752.

Research output: Contribution to journalArticle

Tuckerman, Mark ; Laasonen, Kari ; Sprik, Michiel ; Parrinello, Michele. / Ab initio molecular dynamics simulation of the solvation and transport of H3O+ and OH- ions in water. In: Journal of Physical Chemistry. 1995 ; Vol. 99, No. 16. pp. 5749-5752.
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