Generalized Prediction of Enthalpies of Formation Using DLPNO-CCSD(T) Ab Initio Calculations for Molecules Containing...

The prediction of thermochemical properties such as enthalpies of formation is of crucial importance, both in research and industrial applications, especially for systems involving not well-characterized molecules, such as biomass systems (bio-oils), or systems involving new compounds (new-generation refrigerants). It is highly desirable to obtain an efficient method by which these values can be predicted. Ab initio-based calculations can be very accurate for predicting gas phase thermochemical properties and are usually more versatile than group contribution methods. In this work, we propose a general extension of the work of Paulechka and Kazakov, using very accurate and efficient domain-based local pair natural orbital-coupled cluster theory ab initio calculations, to determine the enthalpies of formation of a broad variety of molecules. New sets of regressed atomic contributions are proposed for a larger group of elements: H, C, N, O, F, S, Cl, and Br. Excellent predictions are obtained for the most studied compounds (bio-oil compounds and refrigerants). © 2019 Wiley Periodicals, Inc.