Abstract

Evolutionary structure searches reveal that at 20 GPa, formic acid (FA) transforms to an orthorhombic ether-chain polymer phase, ruling out hydrogen bond symmetrization, followed by a novel crowned cyclic-ether tetragonal phase above 60 GPa. Emergence of characteristic polyether and new OH stretching modes in infrared experiments validate the findings. Resemblance of polymer chain with a cosmopolymer polyoxymethylene, shows an engrossing multifaceted evolution of FA.

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