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

Physics – Chemical Physics

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submitted to Journal of Chemical Physics

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Monte Carlo methods are used to study the phase transition in ammonium chloride from the orientationally ordered $\delta$ phase to the orientationally disordered $\gamma$ 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-$NVT$ 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.

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