Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

Li, Zhefu; Voth, Gregory A.

doi:10.1039/d0cp00378f

Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

Journal Article · Tue Mar 03 23:00:00 EST 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp00378f· OSTI ID:1803448

Li, Zhefu ^[1]; ^[2]

Univ. of Chicago, IL (United States). Dept. of Chemistry. Chicago Center for Theoretical Chemistry. James Franck Inst. Inst. for Biophysical Dynamics; OSTI
Univ. of Chicago, IL (United States). Dept. of Chemistry. Chicago Center for Theoretical Chemistry. James Franck Inst. Inst. for Biophysical Dynamics

This work employs molecular dynamics simulations to investigate the solvation and transport properties of hydrated excess protons (with a hydronium-like core structure) in non-ionic Igepal CO-520 reverse micelles of various sizes in a non-polar solvent. Multiscale Reactive Molecular Dynamics (MS-RMD) simulations were used to describe vehicular and hopping diffusion during the proton transport process. As detailed herein, an excess proton shows a marked tendency to localize in the interfacial region of micellar water pools. Slow proton transport was observed which becomes faster with increasing micellar size. Further analysis reveals that the slow diffusion of an excess proton is a combined result of slow water diffusion and the low proton hopping rate. This study also confirms that a low proton hopping rate in reverse micelles stems from the interfacial solvation of hydrated excess protons and the immobilization of interfacial water. The low water density in the interfacial region makes it difficult to form a complete hydrogen bond network near the hydrated excess proton, and therefore locks in the orientation of hydrated proton cations. The immobilization of the interfacial water also slows the relaxation of the overall hydrogen bond network.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018648

OSTI ID:: 1803448

Alternate ID(s):: OSTI ID: 1603821
OSTI ID: 2338025
OSTI ID: 1865696

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 19 Vol. 22; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

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