Research Article
Basis Set Effects in the Description of the Cl-O Bond in ClO and XClO/ClOX Isomers (X = H, O, and Cl) Using DFT and CCSD(T) Methods
Table 2
Relative energies (in kcal/mol) of the isomers of ClO
2 and enthalpies of formation at 298K determined from reactions (
16)–(
18).
| | Species | Method | Basis set | ΔH(0) | ΔfH0, reac. (16a) | ΔfH0, reac. (16b) | ΔfH0, reac. (17a) | ΔfH0, reac. (17b) | ΔfH0, reac. (18) | Average |
| | ClOO | G4 | | 2.99 | 28.1 | 28.1 | 26.2 | 26.1 | 27.6 | 27.2 ± 1.8 | | W1BD | | 4.50 | 28.3 | 29.1 | 27.2 | 27.7 | 27.8 | 28.1 ± 1.1 | | B3LYP | Aug6Z | -1.65 | 24.4 | 24.2 | 22.6 | 24.6 | 20.4 | 23.2 ± 3.1 | | PBE0 | Aug6Z | 2.41 | 24.6 | 26.4 | 23.2 | 25.5 | 19.9 | 23.9 ± 4.5 | | M06 | Aug6Z | 3.03 | 23.3 | 25.9 | 23.8 | 24.3 | 22.4 | 23.9 ± 2.4 | | M06-2X | Aug6Z | 1.85 | 30.0 | 31.9 | 28.9 | 29.6 | 28.6 | 29.8 ± 2.3 | | BMK | Aug6Z | -0.26 | 27.5 | 30.2 | 27.0 | 27.9 | 25.7 | 27.7 ± 2.9 | | B2PLYP | Aug6Z | 4.32 | 27.6 | 28.1 | 24.0 | 26.1 | 23.3 | 25.8 ± 3.8 | | CCSD(T) | 6Z | 2.46 | 25.5 | 26.8 | 25.7 | 25.2 | 26.5 | 25.9 ± 1.2 | | W4 | CBS1 | 0.55 | | | | | | 25.1 | | Exper2 | | | | | | | | 23.4 ± 1.0 |
| | OClO | G4 | | | 25.3 | 24.6 | 22.7 | 22.7 | 24.1 | 23.9 ± 2.1 | | W1BD | | | 23.9 | 24.1 | 22.7 | 22.7 | 22.8 | 23.2 ± 1.3 | | B3LYP | Aug6Z | | 25.5 | 25.3 | 23.7 | 25.7 | 21.6 | 24.4 ± 3.1 | | PBE0 | Aug6Z | | 21.7 | 23.5 | 20.3 | 22.6 | 17.0 | 21.0 ± 4.5 | | M06 | Aug6Z | | 19.8 | 22.4 | 20.3 | 20.7 | 18.8 | 20.4 ± 2.4 | | M06-2X | Aug6Z | | 27.9 | 29.8 | 26.8 | 27.5 | 26.5 | 27.7 ± 2.3 | | BMK | Aug6Z | | 27.6 | 30.2 | 27.0 | 27.9 | 25.8 | 27.7 ± 2.9 | | B2PLYP | Aug6Z | | 22.4 | 22.8 | 18.8 | 20.9 | 18.1 | 20.6 ± 3.8 | | CCSD(T) | Aug6Z | | 22.4 | 23.7 | 22.6 | 22.2 | 23.1 | 22.8 ± 1.1 | | W4 | CBS1 | | | | | | | 23.9 | | Exper.3 | | | | | | | | 22.6 ± 0.3 | | Exper.4 | | | | | | | | 23.53 ± 0.24 |
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