Calculating bond dissociation energies of X−H (X=C, N, O, S) bonds of aromatic systems via density functional theory: a detailed comparison of methods
Nguyễn Quang Trung, Ádám Mechler, Nguyễn Thị Hoa, Quan V. Vo
Abstract
In this study, the performance of 17 different density functional theory functionals was compared for the calculation of the bond dissociation energy (BDE) values of X−H (X=C, N, O, S) bonds of aromatic compounds. The effect of the size of the basis set (expansions of 6-31(G)) was also assessed for the initial geometry and zero-point energy calculations, followed by the single-point BDE calculations with different model chemistries with the 6-311 + (3df,2p) basis set. It was found that the size of the basis set for geometry optimization has a much smaller effect on the accuracy of BDE than the choice of functional for the following single-point calculations. The M06-2X, M05-2X and M08−HX functionals yielded highly accurate BDE values compared to experimental data (with the average mean unsigned error MUE = 1.2–1.5 kcal mol −1 ), performing better than any of the other functionals. The results suggest that geometry optimization may be performed with B3LYP functional and a small basis set, whereas the M06-2X, M05-2X and M08-HX density functionals with a suitably large basis set offer the best method for calculating BDEs of ArX−H (X=C, N, O, S) bonds.