Number Dependence of Small‐Crystal Thermodynamic Properties. I

TLDR: In this article, the number dependence of the vibrational entropy for two-and three-dimensional crystallites was calculated by direct integration of the canonical partition function, showing that small-crystal entropies lie within 10k of the predictions of macroscopic thermodynamics.

Abstract: The approach of small‐crystal thermodynamic properties to the large‐crystal limit of thermodynamics is studied numerically. We calculate the number dependence of the vibrational entropy for two‐ and three‐dimensional crystallites by direct integration of the canonical partition function. A simple functional representation of the data shows that small‐crystal entropies lie within 10k of the predictions of macroscopic thermodynamics.