TY - JOUR
T1 - On the connection between proton transport, structural diffusion, and reorientation of the hydrated hydroxide ion as a function of temperature
AU - Ma, Zhonghua
AU - Tuckerman, Mark E.
N1 - Funding Information:
Mark Tuckerman obtained his B.S. in physics from U.C. Berkeley in 1986 and his Ph.D. in physics from Columbia University in 1993, working in the group of Bruce J. Berne. From 1993 to 1994, he held an IBM postdoctoral fellowship at the IBM Forschungslaboratorium in Rüschlikon, Switzerland in the group of Michele Parrinello, and from 1995 to 1996, he held an NSF postdoctoral fellowship in Advanced Scientific Computing at the University of Pennsylvania in Philadelphia in the group of Michael L. Klein. He is currently Professor of Chemistry and Mathematics at New York University. Research interests include reactions in solution, organic reactions on semi-conductor surfaces, and development of the methodology of molecular dynamics, including novel techniques for enhancing conformational sampling and prediction of free energies in biological systems, and the development of new approaches to electronic structure and ab initio molecular dynamics calculations.
Funding Information:
This work was supported by National Science Foundation ( CHE-0704036 and CHE-1012545 ) and by the Department of Energy ( FG05-08OR23334 ). All calculations were carried out at the Computational Center for Nanotechnology Innovation at Rensselaer Polytechnic Institute.
PY - 2011/8/5
Y1 - 2011/8/5
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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U2 - 10.1016/j.cplett.2011.05.066
DO - 10.1016/j.cplett.2011.05.066
M3 - Article
AN - SCOPUS:79960898024
VL - 511
SP - 177
EP - 182
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 4-6
ER -