Calculation of thermodynamic properties of metastable phases of the elements

A chemical bonding model that provides a method of predicting thermodynamic properties of metastable structures of the solid elements is presented. The method involves a Born-Haber-type cycle to calculate the difference in bonding energies between the room temperature stable structures and metastable structures. To carry out the calculations, spectroscopic data are used to determine the promotion energies from the ground state of the gaseous atom to the valence state corresponding to each structure. Such data are available for most elements, but in cases where experimental data are lacking, they are derived using predictive models. Combinations of promotion energies and heats of sublimation are used to determine bonding enthalpies. The contribution of the outer-shell s and p-electrons and the inner-shell d and f electrons to the bonding energies are considered taking into account the crystal field effect upon the bonding abilities of different d and f orbitals This paper was presented at the Thermodynamics and Phase Equilibria of Metastable Phases Symposium at the Spring TMS Meeting, March 1-4, 1992, in San Diego. The symposium was organized by Philip Nash, Illinois Institute of Technology, and Ricardo Schwarz,Los Alamos National Laboratory.