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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

Citation

Vo, Quan V.; Mechler, Adam; Hoa, Nguyen Thi; Trung, Nguyen Quang (2022), Calculating bond dissociation energies of X-H (X = C, N, O, S) bonds of aromatic systems via DFT: A detailed comparison of methods , Dryad, Dataset, https://doi.org/10.5061/dryad.1c59zw3x3

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.

Methods

The dataset was collected during the Gaussian 16 suite of programs at The University of Danang - University of Technology and Education, Vietnam, and La Trobe University, Australia. In this approach, the geometry is optimized, and zero-point energy corrections are calculated with the same model chemistry for all compounds, followed by single-point calculations of BDE values with a range of model chemistries. Consistently, geometry optimizations and frequency calculations were first carried out using B3LYP functional with the 6-31G(d) basis set that was shown before to be the best for this task. Then the single-point energies were calculated using 17 different functionals and the 6-311+G(3df,2p) basis set, followed by comparing calculated and experimental BDE values.

Usage Notes

The data here contains all relevant necessary data to reproduce all results in the paper.

Funding

Vingroup Innovation Foundation (VinIF), Award: VINIF2021.TS.114

Vietnamese Ministry of Education and Training, Award: B2021-DNA-16