Abstract
This chapter discusses a thermodynamic integration technique for computing the Helmholtz free energy of an atomic solid. The basic idea is to transform the solid under consideration reversibly into an Einstein crystal. The orientational degrees of freedom of a molecular solid usually complicate the numerical calculation of the free energy. Although one can still use an Einstein crystal as reference system, it is often nontrivial to find a path to this reference system that is free of phase transitions and not plagued by divergences of the integrand of equation. In such cases, it may be advantageous to use an alternative method that is more robust than the conventional coupling-parameter method. The constraint that the center of mass of the system is fixed eliminates a number of degrees of freedom from the system, which has an effect on the free energy. The change in free energy because of any hard constraint is infinite.
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