High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2023-02, Vol.127 (6), p.1512-1531
• Main Authors: Elliott, Sarah N., Keçeli, Murat, Ghosh, Manik K., Somers, Kieran P., Curran, Henry J., Klippenstein, Stephen J.
• Format: Article
• Language: English
• Subjects: A: Combustion and Plasma Chemistry; chemical calculations; energy; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mathematical methods; molecules; zero point energy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c07248

It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce ΔH f(0 K) values with 2σ uncertainties of 0.2–0.5 kcal mol–1. This set includes the alkanes, hydroperoxides, and alkyl, peroxy, and hydroperoxyalkyl radicals for 17 representative hydrocarbon fuels containing up to 10 heavy atoms with various degrees of branching in the alkane backbone. The CBH-ANL approach, automated in the QTC and AutoMech software suites, builds balanced chemical equations for the calculation of ΔH f(0 K), in which the reference species may be up to five heavy atoms. The high-level ANL0 and ANL1 reference ΔH f(0 K) values are further refined for even the largest of these reference species with a novel laddering approach. We perform a comprehensive quantification of the uncertainties for both the individual reference species (the largest of which is 0.15 kcal mol–1) and the propagation of those uncertainties when used in the calculation of ΔH f(0 K) for the 194 target species. We examine the sensitivity of the predicted ΔH f(0 K) values to (i) electronic energies from various methods, including ωB97X-D/cc-pVTZ, B2PLYP-D3/cc-pVTZ, CCSD­(T)-F12b/cc-pVDZ-F12//B2PLYP-D3/cc-pVTZ, and CCSD­(T)-F12b/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ; (ii) the zero-point vibrational energies (ZPVEs), where we consider harmonic ZPVEs as well as two scaling-based estimates of the anharmonic ZPVEs, all implemented for both ωB97X-D/cc-pVTZ and B2PLYP-D3/cc-pVTZ calculations; (iii) the particular CBH-ANL scheme employed; and (iv) the procedure for choosing the reference conformer for the analyses. The discussion concludes with a summary of the estimated overall uncertainty in the predictions and a validation of the predictions for the alkane subset.