Transferable Ring Corrections for Predicting Enthalpy of Formation of Cyclic Compounds.

Abstract

Computational predictions of the thermodynamic properties of molecules and materials play a central role in contemporary reaction prediction and kinetic modeling. Due to the lack of experimental data and computational cost of high-level quantum chemistry methods, approximate methods based on additivity schemes and more recently machine learning are currently the only approaches capable of supplying the chemical coverage and throughput necessary for such applications. For both approaches, ring-containing molecules pose a challenge to transferability due to the nonlocal interactions associated with conjugation and strain that significantly impact thermodynamic properties. Here, we report the development of a self-consistent approach for parameterizing transferable ring corrections based on high-level quantum chemistry. The method is benchmarked against both the Pedley-Naylor-Kline experimental dataset for C-, H-, O-, N-, S-, and halogen-containing cyclic molecules and a dataset of Gaussian-4 quantum chemistry calculations. The prescribed approach is demonstrated to be superior to existing ring corrections while maintaining extensibility to arbitrary chemistries. We have also compared this ring-correction scheme against a novel machine learning approach and demonstrate that the latter is capable of exceeding the performance of physics-based ring corrections.