TY - JOUR
T1 - Special pair dance and partner selection
T2 - Elementary steps in proton transport in liquid water
AU - Markovitch, Orner
AU - Chen, Hanning
AU - Izvekov, Sergei
AU - Paesani, Francesco
AU - Voth, Gregory A.
AU - Agmon, Noam
PY - 2008/8/7
Y1 - 2008/8/7
N2 - 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 2O] Eigen-complex, via the H5O2+ Zundel-complex, to a H3O+[3H2O] 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.
AB - 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 2O] Eigen-complex, via the H5O2+ Zundel-complex, to a H3O+[3H2O] 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.
UR - http://www.scopus.com/inward/record.url?scp=49649120885&partnerID=8YFLogxK
U2 - 10.1021/jp804018y
DO - 10.1021/jp804018y
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AN - SCOPUS:49649120885
SN - 1520-6106
VL - 112
SP - 9456
EP - 9466
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 31
ER -