Recent developments in ab initio thermodynamics

It has recently become possible to calculate the free energy and other ther modynamic functions of solids and liquids using density functional theory t o treat the quantum mechanics of the electrons. We present the main ideas t hat have made this possible, emphasizing the key role of thermodynamic inte gration and the importance of well-adapted reference systems in the computa tion of the free energy. We show how ab initio methods have been used to ca lculate the melting and other phase-equilibrium properties of simple materi als, and the thermal-equilibrium concentrations of point defects in crystal s. We point out the possibility of adapting techniques that a re already av ailable in order to calculate chemical potentials, solubilities, equilibriu m constants, and other thermodynamic functions that are important in physic al chemistry (C) 2000 John Wiley & Sons, Inc.