jz3c03390_si_002.txt (32.95 kB)
High-Throughput Predictions of Accurate Enthalpies of Formation for Larger Molecules Utilizing the Bond Difference Correction Method
datasetposted on 2024-01-22, 18:41 authored by Huajie Xu, Bo Wang, Lingxian Liao, Yang Wang, Quan Zhu, Haisheng Ren
The prediction of standard enthalpies of formation (EOFs) for larger molecules involves a trade-off between accuracy and cost, often resulting in non-negligible errors. The connectivity-based hierarchy (CBH) and simple bond additivity correction (BAC) are two promising means for evaluating EOFs, although they cannot achieve strict chemical accuracy. Calculated errors in the CBH are confirmed from accumulated systematic errors associated with bond differences in chemical environments. On the basis of a new set of bond descriptors, our developed bond difference correction (BDC) method effectively solves incremental errors with molecular size and inability applications for aromatic molecules. To balance the accuracy between non-aromatic and aromatic molecules, a more accurate BAC-based method with unpaired electrons and p hybrid orbitals (BAC-EP) is developed. With the incorporation of the two methods above, strict chemical accuracy by the largest deviation is achieved at low costs. These universal, ultrafast, and high-throughput methods greatly contribute to self-consistent thermodynamic parameters in combustion mechanisms.
p hybrid orbitalsconsistent thermodynamic parameterslarger molecules utilizinglarger molecules involvestwo promising meansstrict chemical accuracytwo methodschemical environmentsaromatic moleculesunpaired electronsthroughput predictionsstandard enthalpiesoften resultingnew setnegligible errorsmolecular sizelow costslargest deviationinability applicationscombustion mechanismscalculated errorsbond differencesbond descriptorsbased methodbased hierarchyaccurate enthalpies