Monte Carlo Studies of the Orientational Order-Disorder Phase Transition in Solid Ammonium Chloride

Monte Carlo methods are used to study the phase transition in NH4Cl(s) from the orientationally ordered δ phase to the orientationally disordered γ phase. An effective pair potential is used to model the interaction between ions. Thermodynamic properties are computed in the canonical and isothermal-isobaric ensembles. Each ammonium ion is treated as a rigidly rotating body and the lattice is fixed in the low-temperature CsCl geometry. A simple extension of the Metropolis Monte Carlo method is used to overcome quasiergodicity in the rotational sampling. In the constant-NV T calculations the lattice is held rigid; in the constant-NpT calculations the lattice parameter is allowed to fluctuate. In both ensembles the order parameter rapidly falls to zero in the range (200 250)K, suggesting that the model disorders at a temperature in fair agreement with the experimental disordering temperature (243K). Peaks in the heat capacity and thermal expansivity curves are also found in the same temperature range.