1981--MacDonald-R-A-MacDonald-W-M--Cu

Abstract: We have carried out an exact and consistent calculation of the thermodynamic properties of monatomic fcc crystals at high temperatures. These properties are obtained from the Helmholtz free energy of the crystal F(V,T) by means of the appropriate thermodynamic relations. It is crucial to the success of the calculation that we have been able to obtain the volume dependence of the free energy. F(V,T) includes the static lattice energy and the vibrational contributions from the harmonic and lowest-order (cubic and quartic) anharmonic terms in perturbation theory evaluated in the high-temperature limit. The atoms interact via an effective nearest-neighbor central-force potential φ(r). We have calculated the specific heat at constant volume and at constant pressure, the thermal expansion, the coefficient of linear expansion, the isothermal and adiabatic bulk moduli, and the Grüneisen parameter for the following fcc metals: Cu, Ag, Ca, Sr, Al, Pb, and Ni. Good agreement with experiment is obtained in all cases. We discuss the implications of these results for further studies of the properties of metals.