Proton transport mechanism and pathways in the superprotonic phase of M3H(AO4)2 solid acids from ab initio molecular dynamics simulations

Literature Information

Publication Date 2021-07-28
DOI 10.1039/D1CP00757B
Impact Factor 3.676
Authors

Boris V. Merinov, Sergey I. Morozov


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Abstract

The proton transport mechanism in superprotonic phases of solid acids has been a subject of experimental and theoretical studies for a number of years. Despite this, details of the mechanism still need further clarification. In particular in the M3H(AO4)2 family of crystals, where M = NH4, K, Rb, Cs, and A = S, Se, the proton diffusion is mostly considered in the (001) plane, whereas it is relatively high in the [001] direction as well. In this paper, we report the results of our ab initio molecular dynamics simulations of the Cs3H(SeO4)2 superprotonic phase and propose an atomic-level mechanism of proton transport and pathways both in the (001) plane and along the [001] direction. It turned out that structural configurations formed by hydrogen-bonded tetrahedral anions during the proton diffusion are more complicated and diverse than those considered so far in the literature. Our predicted values of the proton conductivity and activation energy agree well with available experimental data. This validates the reliability of the computational results obtained.

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Contents

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DOI: 10.1039/B610770M

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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