Absolute chemical potentials for complex molecules in fluid phases: A centroid reference for predicting phase equilibria

V Khanna and MF Doherty and B Peters, JOURNAL OF CHEMICAL PHYSICS, 153, 214504 (2020).

DOI: 10.1063/5.0025844

Solid-fluid phase equilibria are difficult to predict in simulations because bound degrees of freedom in the crystal phase must be converted to free translations and rotations in the fluid phase. Here, we avoid the solid-to-fluid transformation step by starting with chemical potentials for two reference systems, one for the fluid phase and one for the solid phase. For the solid, we start from the Einstein crystal and transform to the fully interacting molecular crystal. For the fluid phase, we introduce a new reference system, the "centroid," and then transform to gas phase molecules. We illustrate the new calculations by predicting the sublimation vapor pressure of succinic acid in the temperature range of 300 K-350 K.

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