Abstract
The structure and stability of pyrite (100), (210), (110), and (111) surfaces in different sulfur conditions were studied in the framework of GGA(PBE) + U implementations of density functional calculations. The Hubbard U correction was found to be a critical parameter in density functional theory (DFT) calculations to describe pyrite surfaces. With the U correction, the surface energy order for stoichiometric pyrite surfaces is (100) < (210) < (110) < (111), which is different with previous knowledge from conventional DFT and classical force field calculations, but consistent with broken bonds number and shape distribution in natural and synthetic systems in different sulfur conditions. Within the considered surfaces, the stoichiometric (100)-S and non-stoichiometric (111)-3S are the most stable under both S-lean and S-rich conditions, respectively. For relative stable surfaces in different environment, (100)-Fe and (100)-2S reconstruct, but (111)-Fe and (111)-3S show no relaxations while (100)-S, (210)-Fe′, and (210)-2S′ show relaxations to certain degree. Electron transfer from surface Fe to S atom on pyrite during relaxation and reconstruction, forming exemplary surface configuration and chemical composition. These findings reveal the nature of pyrite surfaces in various sulfur conditions, proving fundamental not only for surface-related applications but also for geological indicators of pyrite formation conditions.
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Acknowledgements
The authors acknowledge two anonymous reviewers for their helpful comments and suggestions. This study was supported by the fund from the National Natural Science Foundation of China (Grant nos. 41825003 and 41921003), the Youth Innovation Promotion Association CAS (Grant no. 2021353), the Natural Science Foundation of Guangdong Province, China (Grant no. 2019A1515011303), Guangdong Special Support Program (Grant no. 2019TX05L169), the Tuguangchi Award for Excellent Young Scholar GIG, CAS, and the Science and Technology Planning of Guangdong Province, China (2017B030314175 & 2020B1212060055). This is a contribution No.IS-3001 from GIGCAS.
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Xian, H., Wu, X., Zhu, J. et al. Environmental-sulfur-controlled surface properties of pyrite: a first principles PBE + U study. Phys Chem Minerals 48, 20 (2021). https://doi.org/10.1007/s00269-021-01145-7
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DOI: https://doi.org/10.1007/s00269-021-01145-7