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Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion.
J Phys Chem B. 2019 07 05; 123(26):5536-5544.JP

Abstract

Using a large set of ab initio molecular dynamics trajectories we demonstrate that the mechanistic details of aqueous proton diffusion are insensitive to finite size effects. Furthermore, we show how correlation in the proton hopping direction is related to the presolvation of the hydronium ion. Specifically, we observe a dependence of the probability for the excess proton to return to its previous hydronium ion on whether that hydronium ion was accepting a hydrogen bond from a fourth water molecule at the time the excess proton left. The dynamics of this fourth water molecule was previously linked to the net displacement of the proton, and our analysis shows that this connection is due to the changes in the hopping probability that we calculate. Additionally, we show how our simulated dynamics with correlations that imply a faster time scale are compatible with recent spectroscopy results that point to a slower hopping time scale by looking closely at which proton transitions are being taken into consideration. Finally, we show that the correlation in proton hopping directions is not strongly influenced by interactions among hydronium ions.

Authors+Show Affiliations

Chemistry Division , U.S. Naval Research Laboratory , Washington , D.C. 20375 , United States.Chemistry Division , U.S. Naval Research Laboratory , Washington , D.C. 20375 , United States.

Pub Type(s)

Journal Article
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

31180658

Citation

Fischer, Sean A., and Daniel Gunlycke. "Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion." The Journal of Physical Chemistry. B, vol. 123, no. 26, 2019, pp. 5536-5544.
Fischer SA, Gunlycke D. Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion. J Phys Chem B. 2019;123(26):5536-5544.
Fischer, S. A., & Gunlycke, D. (2019). Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion. The Journal of Physical Chemistry. B, 123(26), 5536-5544. https://doi.org/10.1021/acs.jpcb.9b02610
Fischer SA, Gunlycke D. Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion. J Phys Chem B. 2019 07 5;123(26):5536-5544. PubMed PMID: 31180658.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Analysis of Correlated Dynamics in the Grotthuss Mechanism of Proton Diffusion. AU - Fischer,Sean A, AU - Gunlycke,Daniel, Y1 - 2019/06/21/ PY - 2019/6/11/pubmed PY - 2019/6/11/medline PY - 2019/6/11/entrez SP - 5536 EP - 5544 JF - The journal of physical chemistry. B JO - J Phys Chem B VL - 123 IS - 26 N2 - Using a large set of ab initio molecular dynamics trajectories we demonstrate that the mechanistic details of aqueous proton diffusion are insensitive to finite size effects. Furthermore, we show how correlation in the proton hopping direction is related to the presolvation of the hydronium ion. Specifically, we observe a dependence of the probability for the excess proton to return to its previous hydronium ion on whether that hydronium ion was accepting a hydrogen bond from a fourth water molecule at the time the excess proton left. The dynamics of this fourth water molecule was previously linked to the net displacement of the proton, and our analysis shows that this connection is due to the changes in the hopping probability that we calculate. Additionally, we show how our simulated dynamics with correlations that imply a faster time scale are compatible with recent spectroscopy results that point to a slower hopping time scale by looking closely at which proton transitions are being taken into consideration. Finally, we show that the correlation in proton hopping directions is not strongly influenced by interactions among hydronium ions. SN - 1520-5207 UR - https://www.unboundmedicine.com/medline/citation/31180658/Analysis_of_Correlated_Dynamics_in_the_Grotthuss_Mechanism_of_Proton_Diffusion L2 - https://dx.doi.org/10.1021/acs.jpcb.9b02610 DB - PRIME DP - Unbound Medicine ER -
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