The Relation of Interface Properties and Bulk Phase Stability: Molecular Dynamics Simulations of Carbon Dioxide

• Published in: The journal of physical chemistry. B 2009-04, Vol.113 (14), p.4688-4697
• Main Authors: Kraska, T., Römer, F., Imre, A. R.
• Format: Article
• Language: English
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects; Carbon Dioxide - chemistry; Computer Simulation; Models, Chemical; Particle Size; Pressure; Temperature
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp808789p

The limit of metastability, the so-called spinodal, is calculated for pure carbon dioxide by molecular dynamics simulation. The determination of the spinodal is based on properties of the liquid vapor interface using a recently developed method. This method relates the tangential pressure component through the vapor−liquid interface to the van der Waals loop in the two-phase region of the phase diagram. By application of the thermodynamic stability criteria, the location of the spinodal can be determined. The spinodal determined in this way is called interface spinodal here. Furthermore, the simulation provides equation of state properties in the complete metastable region of the phase diagram. The performance of different correlation equations for the density and the pressure tensor profiles with respect to the estimation of the spinodal is compared. It has been found that the interface spinodal coincides with the thermodynamic mean field spinodal within some reasonable deviation. Finally the influence of the size of the simulation box on the spinodal properties is investigated showing that the temperature-density spinodal data are independent of the interface thickness. Additional simulations using a Lennard-Jones fluid confirm these results over a range of 1.5 orders of magnitude for the systems size. A further result is that interface systems require a very long simulation time in order to obtain reliable results.