Accurate Enthalpies of Formation for PFAS from First-Principles: Combining Different Levels of Theory in a Generalized Thermochemical Hierarchy

The enthalpies of formation are computed for a large number of per- and poly fluoroalkyl substances (PFAS) using a connectivity-based hierarchy (CBH) approach. A combination of different electronic structure methods are used to provide the reference data in a hierarchical manner. The ANL0 method, in conjunction with the active thermochemical tables, provides enthalpies of formation for smaller species with subchemical accuracy. Coupled-cluster theory with explicit correlations are used to compute enthalpies of formation for intermediate species, based upon the ANL0 results. For the largest PFAS, including perfluorooctanoic acid (PFOA) and heptafluoropropylene oxide dimer acid (GenX), coupled-cluster theory with local correlations is used. The sequence of homodesmotic reactions proposed by the CBH are determined automatically by a new open-source code, AutoCBH. The results are the first reported enthalpies of formation for the majority of the species. A convergence analysis and global uncertainty quantification confirm that the enthalpies of formation at 0 K should be accurate to within ±5 kJ/mol. This new approach is not limited to PFAS, but can be applied to many chemical systems

Accurate Enthalpies of Formation for PFAS from First-Principles: Combining Different Levels of Theory in a Generalized Thermochemical Hierarchy

The enthalpies of formation are computed for a large number of per- and poly fluoroalkyl substances (PFAS) using a connectivity-based hierarchy (CBH) approach. A combination of different electronic structure methods are used to provide the reference data in a hierarchical manner. The ANL0 method, in conjunction with the active thermochemical tables, provides enthalpies of formation for smaller species with subchemical accuracy. Coupled-cluster theory with explicit correlations are used to compute enthalpies of formation for intermediate species, based upon the ANL0 results. For the largest PFAS, including perfluorooctanoic acid (PFOA) and heptafluoropropylene oxide dimer acid (GenX), coupled-cluster theory with local correlations is used. The sequence of homodesmotic reactions proposed by the CBH are determined automatically by a new open-source code, AutoCBH. The results are the first reported enthalpies of formation for the majority of the species. A convergence analysis and global uncertainty quantification confirm that the enthalpies of formation at 0 K should be accurate to within ±5 kJ/mol. This new approach is not limited to PFAS, but can be applied to many chemical systems