Improved modeling of two-dimensional transitions in dense phases on crystalline surfaces. Krypton–graphite system

Journal Article · Sat Feb 21 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4908035· OSTI ID:22416152

This paper presents a refined technique to describe two-dimensional phase transitions in dense fluids adsorbed on a crystalline surface. Prediction of parameters of 2D liquid–solid equilibrium is known to be an extremely challenging problem, which is mainly due to a small difference in thermodynamic functions of coexisting phases and lack of accuracy of numerical experiments in case of their high density. This is a serious limitation of various attempts to circumvent this problem. To improve this situation, a new methodology based on the kinetic Monte Carlo method was applied. The methodology involves analysis of equilibrium gas–liquid and gas–solid systems undergoing an external potential, which allows gradual shifting parameters of the phase coexistence. The interrelation of the chemical potential and tangential pressure for each system is then treated with the Gibbs–Duhem equation to obtain the point of intersection corresponding to the liquid/solid–solid equilibrium coexistence. The methodology is demonstrated on the krypton–graphite system below and above the 2D critical temperature. Using experimental data on the liquid–solid and the commensurate–incommensurate transitions in the krypton monolayer derived from adsorption isotherms, the Kr–graphite Lennard–Jones parameters have been corrected resulting in a higher periodic potential modulation.

• OSTI ID: 22416152
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ADSORPTION ISOTHERMS
CRITICAL TEMPERATURE
EQUILIBRIUM
GRAPHITE
KRYPTON
LIQUIDS
MODULATION
MONTE CARLO METHOD
PERIODICITY
PHASE TRANSFORMATIONS
POTENTIALS
SOLIDS
SURFACES
TWO-DIMENSIONAL CALCULATIONS
TWO-DIMENSIONAL SYSTEMS