Recent developments in ab initio thermodynamics

Abstract

It has recently become possible to calculate the free energy and other thermodynamic functions of solids and liquids using density functional theory to treat the quantum mechanics of the electrons. We present the main ideas that have made this possible, emphasizing the key role of thermodynamic integration and the importance of well-adapted reference systems in the computation of the free energy. We show how ab initio methods have been used to calculate the melting and other phase-equilibrium properties of simple materials, and the thermal-equilibrium concentrations of point defects in crystals. We point out the possibility of adapting techniques that are already available in order to calculate chemical potentials, solubilities, equilibrium constants, and other thermodynamic functions that are important in physical chemistry. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 871–879, 2000