BAC-MP4 Predictions of Thermochemical Data for C1 and C2 Stable and Radical Hydrofluorocarbons and Oxidized Hydrofluorocarbons

Abstract

An ab initio bond additivity corrected quantum chemistry procedure has been applied to the development of a data base for thermochemistry of C/H/F/O species. This information has been used to construct a chemical kinetic mechanism for the prediction of the behavior of fluorocarbons as flame suppressants, with clear applications to plasma and atmospheric chemistry as well. Bond additivity corrected (BAC) Moller−Plesset fourth-order perturbation theory (MP4) calculations have been performed to obtain a large body of thermochemical data on about 100 closed and open shelled fluorocarbon species. For about 70 of these species, literature values for enthalpies of formation were available for comparison to the calculated values. The average difference between the calculated and literature values was about 9 kJ/mol. The results indicate that the BAC-MP4 procedure can provide energies that are comparable in accuracy to most experimentally derived values, at lower computational costs relative to other more computationally expensive ab initio molecular orbital methods. This work provides a substantial data base of thermochemical data for fluorinated hydrocarbons constructed in a self-consistent manner.