Two methods for calculating the effect of vacancy defects on the free energy of harmonic solids

Abstract
Two methods are developed for calculating the change in vibrational free energy ΔF of a solid with first-neighbor interactions which results from the introduction of a vacancy defect. One method employs a summation of central moments calculated from closed walks. From this well-defined method a more intuitive cell cluster technique is derived. As an example, both methods are used to calculate ΔF for the triangular lattice. Each method yields the result ΔF/kT=−1.9.

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