Anharmonic force field, structure, and thermochemistry of CF2 and CCl2

Abstract

The anharmonic force field up to quartic terms has been calculated for both CF₂ and CCl₂ at the CCSD(T) level of theory with large basis sets. The calculated spectroscopic parameters are in excellent agreement with the available experimental data. The equilibrium structure of CCl₂ has been calculated at the CCSD(T) level of theory with the cc-pV5Z basis set (including core correlation corrections). It is in excellent agreement with the semi-experimental equilibrium structure derived from the experimental rotational constants and the ab initio rovibrational interaction parameters. The heats of formation of CF₂ and CCl₂ have been calculated using the W2 method and are −193.43 and 227.96 kJ mol⁻¹, respectively.