Theoretical and Computational Chemistry

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling



Standard enthalpies, entropies, and heat capacities are calculated for 16,813 halocarbons using an automated high-fidelity thermochemistry workflow. This workflow generates conformers at density functional tight binding (DFTB) level, optimizes geometries, calculates harmonic frequencies, and performs 1D hindered rotor scans at DFT level, and computes electronic energies at G4 level. The computed enthalpies of formation for 400 molecules show good agreement with literature references, but the majority of the calculated species have no reference in the literature. Thus, this work presents the most accurate thermochemistry for many halocarbons to date. This new data set is used to train an extensive ensemble of group additivity values and hydrogen bond increment groups within the Reaction Mechanism Generator (RMG) framework. On average, the new group values estimate standard enthalpies for halogenated hydrocarbons within 3 kcal/mol of their G4 values. A significant contribution towards automated mechanism generation of halocarbon combustion, this research provides thermochemical data for thousands of novel halogenated species and presents a self-consistent set of halogen group additivity values.


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