Eliminating Systematic Errors in DFT via Connectivity-Based Hierarchy: Accurate Bond Dissociation Energies of Biodiesel Methyl Esters.

Abstract

We present a computational study focusing on the determination of accurate bond dissociation energies (BDEs) involved in the combustion of biodiesel methyl esters. We have adapted our previously developed efficient error-cancellation protocols, based on the systematic "connectivity-based hierarchy" (CBH), to derive accurate BDEs of biodiesel molecules at a modest computational cost. Using DFT energies on the full biodiesel molecule in conjunction with accurate G4 energies on the small fragments involved in the CBH reaction schemes, systematic errors in the DFT methods can be cancelled efficiently. Herein, we apply our G4-corrected ΔCBH-2 and ΔCBH-3 schemes in conjunction with several popular DFT methods to determine accurate bond dissociation energies of different C-C, C-H, and C-O bonds in biodiesel surrogate molecules. We first evaluate the performance of different DFT methods using a test set of 21 reactions involving various bond dissociations in small to medium biodiesel surrogates (up to methyl decanoate, a C10-methyl ester) by calibration against accurate values calculated with multireference methods (MRACPF2), reported by Carter and co-workers. The CBH-2 corrections for all tested dispersion-corrected functionals yield mean absolute deviations (MADs) in a narrow range of 1.3-1.5 kcal/mol, the best performance being obtained for B97-D3 and ωB97X-D functionals (MAD = 1.3 kcal/mol). Further, significant improvement yielding a MAD of only 0.9 kcal/mol is obtained using the G4-corrected CBH-3 scheme. Finally, the protocol has been applied to derive accurate BDEs of eight different bonds in the larger biodiesel molecule, methyl linolenate, yielding a MAD of only 1.13 kcal/mol using the ΔCBH-3 error correction scheme. The results suggest that our protocol in conjunction with different DFT methods should be broadly applicable to yield accurate BDEs for a variety of large biodiesel molecules.