Title: Tracking Aqueous Proton Transfer by Two-Dimensional Infrared Spectroscopy and ab Initio Molecular Dynamics Simulations

Abstract

Proton transfer in water is ubiquitous and a critical elementary event which, via proton hopping between water molecules, enables protons to diffuse much faster than other ions. The problem of the anomalous nature of proton transport in water was first identified by Grotthuss over 200 years ago. In spite of a vast amount of modern research effort, there are still many unanswered questions about proton transport in water. An experimental determination of the proton hopping time has remained elusive due to its ultrafast nature and the lack of direct experimental observables. Here, we use 2D IR spectroscopy to extract the chemical exchange rates between hydronium and water in acid solutions using a vibrational probe, methyl thiocyanate. Ab initio molecular dynamics (AIMD) simulations demonstrate that the chemical exchange is dominated by proton hopping. The observed experimental and simulated acid concentration dependence then allow us to extrapolate the measured single step proton hopping time to the dilute limit, which, within error, gives the same value as inferred from measurements of the proton mobility and NMR line width analysis. In addition to obtaining the proton hopping time in the dilute limit from direct measurements and AIMD simulations, the results indicate that proton hoppingmore » in dilute acid solutions is induced by the concerted multi-water molecule hydrogen bond rearrangement that occurs in pure water. This proposition on the dynamics that drive proton hopping is confirmed by a combination of experimental results from the literature.« less

Authors:

Yuan, Rongfeng  ^[1];

• Search DOE PAGES for author "Yuan, Rongfeng"
• Search DOE PAGES for ORCID "0000-0002-6572-2472"

Napoli, Joseph A. ^[1]; Yan, Chang ^[1]; Marsalek, Ondrej  ^[2];

• Search DOE PAGES for author "Marsalek, Ondrej"
• Search DOE PAGES for ORCID "0000-0002-8624-8837"

Markland, Thomas E.  ^[1];

• Search DOE PAGES for author "Markland, Thomas E."
• Search DOE PAGES for ORCID "0000-0002-2747-0518"

Fayer, Michael D.  ^[1]

• Search DOE PAGES for author "Fayer, Michael D."
• Search DOE PAGES for ORCID "0000-0002-0021-1815"

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+ Show Author Affiliations

1. Department of Chemistry, Stanford University, Stanford, California 94305, United States
2. Charles University, Faculty of Mathematics and Physics, Ke Karlovu 3, 121 16 Prague 2, Czech Republic

Publication Date:

Thu May 23 00:00:00 EDT 2019

Research Org.:

Stanford Univ., CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:

1515581

Alternate Identifier(s):

OSTI ID: 1544670; OSTI ID: 1603519; OSTI ID: 1784970

Grant/Contract Number:  

AC02-05CH11231; SC0014437; FG03-84ER13251; FG02-84ER13251

Resource Type:

Published Article

Journal Name:

ACS Central Science

Additional Journal Information:

Journal Name: ACS Central Science Journal Volume: 5 Journal Issue: 7; Journal ID: ISSN 2374-7943

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 14 SOLAR ENERGY