The Phase Diagram of Carbon Dioxide from Correlation Functions and a Many-body Potential

TL;DR

This study develops a computational method combining molecular dynamics and the Two-Phase Thermodynamics approach to accurately determine the phase diagram of CO2, emphasizing the importance of many-body quantum charge effects.

Contribution

The paper introduces a new many-body, fluctuating charge model for CO2 that improves phase diagram predictions by incorporating quantum mechanical charge reorganization effects.

Findings

Accurate phase boundaries for CO2 obtained using the 2PT method.

The new CO2-Fq model matches experimental phase behavior across the phase diagram.

Highlighting the importance of quantum charge effects in molecular phase stability.

Abstract

The phase stability and equilibria of carbon dioxide is investigated from 125 -- 325K and 1 -- 10,000 atm using extensive molecular dynamics (MD) simulations and the Two-Phase Thermodynamics (2PT) method. We devise a direct approach for calculating phase diagrams in general, by considering the separate chemical potentials of the isolated phase at specific points on the P-T diagram. The unique ability of 2PT to accurately and efficiently approximate the entropy and Gibbs energy of liquids thus allows for assignment of phase boundaries from relatively short ($\mathrm{\sim}$ 100ps) MD simulations. We validate our approach by calculating the critical properties of the flexible Elementary Physical Model 2 (FEPM2), showing good agreement with previous results. We show, however, that the incorrect description of the short-range Pauli force and the lack of molecular charge polarization leads to deviations from experiments at high pressures. We thus develop a many-body, fluctuating charge model for CO${}_{2}$, termed CO${}_{2}$-Fq, from high level quantum mechanics (QM) calculations, that accurately captures the condensed phase vibrational properties of the solid (including the Fermi resonance at 1378 cm${}^{-1}$) as well as the diffusional properties of the liquid, leading to overall excellent agreement with experiments over the entire phase diagram. This work provides an efficient computational approach for determining phase diagrams of arbitrary systems and underscore the critical role of QM charge reorganization physics in molecular phase stability.