  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.
