Equilibrium polymerization and gas-liquid critical behavior in the Stockmayer fluid

Abstract

We develop a simple theory explaining the dependence of the gas-liquid critical point in the Stockmayer fluid on dipole strength. The theory is based on the Flory-Huggins lattice description for polymer systems in conjunction with a transfer matrix model for isolated chains of reversibly assembled dipolar particles. We find that the shift of the critical point as a function of dipole strength, which originally was found in computer simulation, strongly resembles the critical point shift as a function of chain length in ordinary linear polymer systems. In particular, the decrease of the critical density with increasing dipole strength is a consequence of the existence of reversible chains near criticality. In addition we report simulation results for gas-liquid critical points well above the limiting dipole strength found previously.