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Calculating bond dissociation energies of X-H (X = C, N, O, S) bonds of aromatic systems via DFT: A detailed comparison of methods

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May 20, 2022 version files 50.96 KB

Abstract

In this study, the bond dissociation energy (BDE) values of X-H (X = C, N, O, S) bonds of aromatic compounds were computed by using 17 different DFT functionals, namely M08-HX, M06-2X, M05-2X, M06, M05, BMK, MPW1B95, B1B95, B98, B97-2, LC-wPBE, B3LYP, cam-B3LYP, B2PLYP, MPWB1K, BB1K, BB95, within the basis set range 6-31G(d), 6-31+G(d), 6-31+G(d,p), 6-311G(d,p) and 6-311++G(d,p). The results show that the 6-31G(d) is the most convenient basis set to perform the BDE calculations with sufficient accuracy compared to the relevant experimental BDEs. The M06-2X, M05-2X, and M08-HX functionals gave highly accurate BDE values (with the average mean unsigned error MUE = 1.2-1.5 kcal/mol), performing better than the other functionals. The results suggest that the M06-2X, M05-2X, and M08-HX density functionals in the combined DFT/6-311+G(3df,2p)//B3LYP/6-31G(d) model chemistry offer the best method for calculating BDEs of ArX-H (X = C, N, O, S) bonds.