Select frontier molecular orbital (MO) energies, ionization potential (IP), and electron affinity (EA) as determined at the OT-LC-ωPBE/cc-PVDZ level of theory. All energies are in eV. The tuned ω parameters for the OT-LC-ωPBE functionals are also provided for reference.
| Molecule | ω | HOMO | LUMO | Δ(HOMO − LUMO) | IP | EA | Δ(IP − EA) |
|---|---|---|---|---|---|---|---|
| L7-methyl | 0.201 | −9.31 | −3.03 | 6.27 | 8.52 | −3.80 | 4.72 |
| TCNQ | 0.236 | −9.73 | −3.07 | 6.67 | 9.11 | −3.63 | 5.49 |
| TCNE | 0.324 | −11.99 | −2.82 | 9.17 | 11.63 | −3.28 | 8.35 |
| TCNB | 0.278 | −11.32 | −1.91 | 9.41 | 10.86a | −2.40 | 8.46a |
| DTP (9) | 0.182 | −8.55 | −2.60 | 5.95 | 7.69 | −3.42 | 4.27 |
| DSP (10) | 0.180 | −8.50 | −2.53 | 5.98 | 7.64 | −3.37 | 4.27 |
a
At the OT-LC-ωPBE/cc-PVDZ level of theory, the optimized geometry of the TCNB cation resulted in one negative frequency at −292 cm−1. Multiple attempts to overcome this negative frequency were unsuccessful. Tests with different functionals and at the HF/cc-PVDZ level of theory suggest that it is the amount of Hartree–Fock (HF) exchange in the functional that leads to the non-minimum structure.