Critical evaluation of the enthalpies of formation for fluorinated compounds using experimental data and high-level ab initio calculations.

Abstract

The ab initio method for prediction of the enthalpies of formation for CHON-containing organic compounds proposed earlier (J. Chem. Theory Comput. 2018, 14, 5920-5932) has been extended to their fluorinated derivatives. A single experimental Δf H o m is typically available for compounds in this scope. Thus, a priori evaluation of the data quality was found to be inefficient despite all available experimental data for C1─C3 hydrofluorocarbons and 34 data points for medium-size organofluorine compounds being considered. The training set was derived by analyzing consistency of the experimental and predicted values and removal of outliers. Significant issues in the experimental data, including inconsistency across different laboratories, were identified and potential causes for these problems were discussed. A conservative estimate of uncertainty for the experimental Δf H o m of organofluorine compounds was proposed.