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Dichtefunktionalrechnungen, Entropie, Gemischtvalente Verbindungen, Festkörperreaktionen
Abstract:
Abstract Synthesis of elusive K4O6 has disclosed implications of crucial relevance for new solid materials discovery. K4O6 forms in equilibrium from K2O2 and KO2, in an all-solid state, endothermic reaction at elevated temperature, undergoing back reaction upon cooling to ambient conditions. This tells that the compound is stabilized by entropy alone. Analyzing possible entropic contributions reveals that the configurational entropy of ?localized? electrons, i.e., of polaronic quasi-particles, provides the essential contribution to the stabilization. We corroborate this assumption by measuring the relevant heats of transformation and tracking the origin of entropy of formation computationally. These findings challenge current experimental and computational approaches towards exploring chemical systems for new materials by searching the potential energy landscape: one would fail in detecting candidates that are crucially stabilized by the configurational entropy of localized polarons.
