biostudies-literatureBenkada ANational Research Foundation Singaporee202202318https://www.ebi.ac.uk/biostudies/studies/S-EPMC10099607biostudies-literatureUnknown29(1)A highly unusual solid-state epitaxy-induced phase transformation of Na₄ SnS₄  ⋅ 14H₂ O (I) into Na₄ Sn₂ S₆  ⋅ 5H₂ O (II) occurs at room temperature. Ab initio molecular dynamics (AIMD) simulations indicate an internal acid-base reaction to form [SnS₃ SH]^3- which condensates to [Sn₂ S₆ ]^4- . The reaction involves a complex sequence of O-H bond cleavage, S^2- protonation, Sn-S bond formation and diffusion of various species while preserving the crystal morphology. In situ Raman and IR spectroscopy evidence the formation of [Sn₂ S₆ ]^4- . DFT calculations allowed assignment of all bands appearing during the transformatioChemistry (Weinheim an der Bergstrasse, Germany)Room-Temperature Solid-State Transformation of Na₄ SnS₄  ⋅ 14H₂ O into Na₄ Sn₂ S₆  ⋅ 5H₂ O: An Unusual Epitaxial Reaction Including Bond Formation, Mass Transport, and Ionic Conductivity.PMC10099607AcRF grant R-284-000-250-114Reinsch HA Engesser TNather CAdams SZinkevich TLuhmann HBenkada AHartmann FIndris SBensch WfalseRoom-Temperature Solid-State Transformation of Na₄ SnS₄  ⋅ 14H₂ O into Na₄ Sn₂ S₆  ⋅ 5H₂ O: An Unusual Epitaxial Reaction Including Bond Formation, Mass Transport, and Ionic Conductivity.A highly unusual solid-state epitaxy-induced phase transformation of Na₄ SnS₄  ⋅ 14H₂ O (I) into Na₄ Sn₂ S₆  ⋅ 5H₂ O (II) occurs at room temperature. Ab initio molecular dynamics (AIMD) simulations indicate an internal acid-base reaction to form [SnS₃ SH]^3- which condensates to [Sn₂ S₆ ]^4- . The reaction involves a complex sequence of O-H bond cleavage, S^2- protonation, Sn-S bond formation and diffusion of various species while preserving the crystal morphology. In situ Raman and IR spectroscopy evidence the formation of [Sn₂ S₆ ]^4- . DFT calculations allowed assignment of all bands appearing during the transformatio2023-01-01T00:00:00Z2023 Jan2025-07-08T03:10:53.17Z2025-04-05T21:11:54.968ZS-EPMC100996073621465810.1002/chem.202202318