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- W2024153560 abstract "The solid-state polymerization of S2N2 to (SN)x is investigated as it relates to the molecular, crystallographic, and defect structures of this superconducting polymer. The least motion principle predicts that polymerization should occur by a nonunique reaction to form cis–trans polymer chains normal to the 21 axis of the precursor phase. The origin of the disordered structure observed in partially polymerized S2N2 is explained by the occurrence of two symmetry equivalent reaction modes, which produce chains related by a center of symmetry. Both monomer and polymer phases have 2/m point symmetry, but the twofold axes are orthogonal. Consequently, the statistical symmetry of (SN)x is mmm, which is manifest (as a function of thermal history) either by twinning, molecular scale disorder, the statistical nature of the relationship between S2N2 and (SN)x crystal orientations, or a combination of these possibilities. In agreement with prediction, this symmetry is produced by equal population of the twin crystals previously observed in (SN)x. Coordinates associated with disordered chains in partially polymerized S2N2 are successfully predicted by this reaction theory. Fractionally occupied sites are observed in the polymer corresponding to (SN)x chains with different orientations, but the same chain axis direction. The geometry of one of these chains is substantially different from that of the major chain component." @default.
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- W2024153560 date "1976-03-01" @default.
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- W2024153560 title "A theoretical investigation of the solid‐state synthesis of (SN)<sub><i>x</i></sub>" @default.
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- W2024153560 doi "https://doi.org/10.1063/1.432470" @default.
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