{"title":"Proton Diffusion in Orthorhombic Perovskite Sulfides","authors":"Stefan Walder, Aurelie Gueguen, Denis Kramer","doi":"10.1021/acs.chemmater.4c01841","DOIUrl":null,"url":null,"abstract":"The proton mobility in perovskite sulfides is investigated. Both stable as well as unstable compounds are considered to cover a wide range of ABS<sub>3</sub> compounds, the latter were selected based on a preferably small energy difference to the thermodynamic phase equilibrium. Density functional theory (DFT) is used to analyze all possible metastable hydrogen positions within the (001) and (110)/(11̅0) planes spanned by the sulfur atoms. The nudged elastic band (NEB) method is used to determine the activation energy barriers between neighboring hydrogen sites. From the hydrogen positions and the activation energies, the diffusion rate is calculated with an approach based on the Markovian master equation. Proton mobility is analyzed in detail for a subset of compounds, while a simplified analysis of the <i>zigzag</i>-paths in the prominent [001] and [010] directions is used to explore a wider chemical space. Room temperature diffusion coefficients of the order of 10<sup>–6</sup> cm<sup>2</sup>/s are predicted to be feasible in Zr-based compounds. The A- and B-site occupants influence mobility mainly due to their impact on crystallography, because symmetry-breaking distortions that reduce the S–S distance have a leading influence on reducing activation energies, but they also induce significant anisotropy.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"35 1","pages":""},"PeriodicalIF":7.2000,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acs.chemmater.4c01841","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The proton mobility in perovskite sulfides is investigated. Both stable as well as unstable compounds are considered to cover a wide range of ABS3 compounds, the latter were selected based on a preferably small energy difference to the thermodynamic phase equilibrium. Density functional theory (DFT) is used to analyze all possible metastable hydrogen positions within the (001) and (110)/(11̅0) planes spanned by the sulfur atoms. The nudged elastic band (NEB) method is used to determine the activation energy barriers between neighboring hydrogen sites. From the hydrogen positions and the activation energies, the diffusion rate is calculated with an approach based on the Markovian master equation. Proton mobility is analyzed in detail for a subset of compounds, while a simplified analysis of the zigzag-paths in the prominent [001] and [010] directions is used to explore a wider chemical space. Room temperature diffusion coefficients of the order of 10–6 cm2/s are predicted to be feasible in Zr-based compounds. The A- and B-site occupants influence mobility mainly due to their impact on crystallography, because symmetry-breaking distortions that reduce the S–S distance have a leading influence on reducing activation energies, but they also induce significant anisotropy.
期刊介绍：
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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