Self-Consistent Component Increment Theory for Predicting Enthalpy of Formation
Qiyuan Zhao, Brett Matthew Savoie · Journal of Chemical Information and Modeling · 2020
The gas-phase enthalpy of formation (Δ H f ) plays a fundamental role in predicting reaction thermodynamics and constructing kinetic models. With advances in computational power and method development, chemically accurate quantum chemistry methods that can predict Δ H f values for small molecules are available; however, large molecules are still out of reach. Increment theories provide a means of extending the prediction capability of high-level methods by decomposing the molecular Δ H f into the additive contributions from individual atoms, bonds, groups, or components. Here, we introduce a novel component increment theory, topology-automated force–field interaction component increment theory (TCIT), in which all component contributions are derived exclusively from Gaussian-4 (G4) results for algorithmically generated model compounds. In a benchmark evaluation of noncyclic compounds from the Pedley, Naylor, and Kline experimental Δ H f dataset, TCIT exhibits consistently lower signed and absolute errors compared with the conventional Benson group increment theory (BGIT). These results pave the way for future extensions of TCIT to ring-containing, ionic, and radical species for which experimental data scarcity currently limits the application of BGIT.