Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 112, Issue 31, Pages 9456-9466Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp804018y
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- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1036464] Funding Source: National Science Foundation
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Conditional and time-dependent radial distribution functions reveal the details of the water structure surrounding the hydronium during the proton mobility process. Using this methodology for classical multistate empirical valence bond (MS-EVB) and ab initio molecular dynamics trajectories, as well as quantal MS-EVB trajectories, we supply statistical proof that proton hops in liquid water occur by a transition from the H3O+[3H(2)O] Eigen-complex, via the H5O2+ Zundel-complex, to a H3O+[3H(2)O] centered on a neighboring water molecule. In the resting period before a transition, there is a distorted hydronium with one of its water ligands at a shorter distance and another at a longer distance than average. The identity of this special partner interchanges rapidly within the three first-shell water ligands. This is coupled to cleavage of an acceptor-type hydrogen bond. Just before the transition, a partner is selected by an additional translation of the H3O+ moiety in its direction, possibly enabled by loosening of donor-type hydrogen bonds on the opposite side. We monitor the transition in real time, showing how the average structure is converted to a distorted H5O2+ cation constituting the transitional complex for proton hopping between water molecules.
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