STABILITIES OF HYPERVALENT CHLORINE FLUORIDES (CLF3, CLF5 AND CLF7)

Ab initio electronic structure calculations have been performed on the hypervalent chlorine fluorides, ClF3, ClF5 and ClF7 in order to determine their thermodynamic stabilities with respect to dissociation to ClF and nF2. Results of the calculations, which included electron correlation and utilized extended basis sets, led to estimates of 24 and 42 kcal/mol for the predicted stability of ClF3 and ClF5, respectively. Calculations on the D5h symmetry structure of ClF7 indicate that this system is 16 kcal/mol unstable. Although this molecule appears to be a minimum at the Hartree-Fock level, the question of whether this molecule is a true minimum on the correlated potential energy surface was not fully addressed.