Thermal features and thermochemistry of hexachlorohafnates of nitrogen aromatic bases

Hexachlorohafnates of pyridine and its three methyl-substituted derivatives were synthesized and examined by the thermoanalytical methods. The van't Hoff equation employed for the thermogravimetric αvs. T dependencies enabled evaluation of the heats of the thermal dissociation and subsequently enthalpies of formation and crystal lattice energies of the salts. Geometry and energy of formation of HfCl ₆ ^2? was determined at the ab initio Hartree-Fock SCF level, using all electron MINI basis set augmented with standard polarization functions (MINI^*). Electron correlation was considered at the MP2 level. Thermodynamic characteristics for the latter species were also obtained combining ab initio results with those of statistical thermodynamics. The usefulness of theoretical methods in examination of solid state energetics is briefly discussed.