We present a detailed investigation of observable properties associated with the relative stability of the rocksalt and cesium chloride phases in the Na, K, Rb, Cs; Cl, Br, I) crystal family. Thermodynamic transition pressures and differences in total energies, volumes, and bulk moduli at zero and transition pressures are computed following a localized Hartree-Fock method. The arrangement of the data in clear trends is shown to be mainly dominated by the cation atomic number. This behavior is well interpreted in terms of a variety of microscopic arguments that emerge from (i) the evaluation of the energy Hessian at the and points and (ii) the decomposition of the energy and pressure in anionic and cationic classical and quantum-mechanical contributions.
1 February 1998 in The Journal of Physical Chemistry A