Back to Search
Start Over
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
- Source :
- Royal Society Open Science, Vol 9, Iss 6 (2022)
- Publication Year :
- 2022
- Publisher :
- The Royal Society, 2022.
-
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.
- Subjects :
- DFT
functional
bond dissociation energy
aromatic compounds
M06-2X
M08-HX
Science
Subjects
Details
- Language :
- English
- ISSN :
- 20545703
- Volume :
- 9
- Issue :
- 6
- Database :
- Directory of Open Access Journals
- Journal :
- Royal Society Open Science
- Publication Type :
- Academic Journal
- Accession number :
- edsdoj.1309ae2773774452940afb79cafdbb14
- Document Type :
- article
- Full Text :
- https://doi.org/10.1098/rsos.220177