Persistent local order heterogeneity in the supercritical carbon dioxide

Abstract

The supercritical state is currently viewed as uniform and homogeneous on the pressure-temperature phase diagram in terms of physical properties. Here, we study structural properties of the supercritical carbon dioxide, and discover the existence of persistent medium-range order correlations which make supercritical carbon dioxide non-uniform and heterogeneous on an intermediate length scale, a result not hitherto anticipated. We report on the carbon dioxide heterogeneity shell structure where, in the first shell, both carbon and oxygen atoms experience gas-like type inter- actions with short range order correlations, while within the second shell oxygen atoms essentially exhibit liquid-like type of interactions with medium range order correlations due to localisation of transverse-like phonon packets. We show that the local order heterogeneity remains in the three phase-like equilibrium within very wide temperature range. Importantly, we highlight a catalytic role of atoms inside the nearest neighbor heterogeneity shell in providing a mechanism for diffusion in the supercritical carbon dioxide on an intermediate length scale. Finally, we discuss important implications for answering the intriguing question whether Venus may have had carbon dioxide oceans and urge for an experimental detection of this persistent local order heterogeneity.

arXiv comment5 pages, 6 figures

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• "Two-phase" thermodynamics of the Frenkel line
• Topological Characterization of Rigid-Nonrigid Transition across the Frenkel Line
• The Physical Origin of the Venus Low Atmosphere Chemical Gradient
• Topological generalization of the rigid-nonrigid transition in soft-sphere and hard-sphere fluids
• Revisiting the question of what instantaneous normal modes tell us about liquid dynamics
• Physical Signatures of Supercritical Fluid Boundaries