Comparison of ReaxFF, DFTB, and DFT for Phenolic Pyrolysis. 2. Elementary Reaction Paths

CW Bauschlicher and TT Qi and EJ Reed and A Lenfant and JW Lawson and TG Desai, JOURNAL OF PHYSICAL CHEMISTRY A, 117, 11126-11135 (2013).

DOI: 10.1021/jp408113w

Reaction paths for the loss of CO, H-2, and H2O from atomistic models of phenolic resin are determined using the hybrid B3LYP approach. B3LYP energetics are confirmed using CCSD(T). The energetics along the B3LYP paths are also evaluated using the PW91 generalized gradient approximation (GGA), the more approximate self-consistent charge density functional tight binding (SCC-DFTB), and the reactive force field (ReaxFF). Compared with the CCSD(T)/cc-pVTZ level for bond and reaction energies and barrier heights, the B3LYP, PW91, DFTB(mio), DFTB(pbc), and ReaxFF have average absolute errors of 3.8, 5.1, 17.4, 13.2, and 19.6 kcal/mol, respectively. The PW91 is only slightly less accurate than the B3LYP approach, while the more approximate approaches yield somewhat larger errors. The SCC-DFTB paths are in better agreement with B3LYP than are those obtained with ReaxFF.

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