High-Throughput Predictions of Accurate Enthalpies of Formation for Larger Molecules Utilizing the Bond Difference Correction Method

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.