ωB97XD/6-31G** relative energies ΔE [eV] with respect to the electronic ground state (in bold), 〈S2〉 expectation values, energy gap Δg, edge binding energies Eeb [eV] (Gibbs free energy change [eV] in parentheses) of the QD2 with the different edge functionalization. Calculations were performed in various spin states S represented by multiplicity M and magnetic moment m [μB/QD]. The superscripts α and β stand for alpha and beta LUMO–HOMO gaps, respectively.
| S | M | m | O | F | OH | ||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| ΔE | 〈S2〉 | Δ g | ΔE | 〈S2〉 | Δ g | ΔE | 〈S2〉 | Δ g | |||
| 0 | Singlet CS | 0 | 0.65 | 0.00 | 4.89 | 0.94 | 0.00 | 4.36 | 0.65 | 0.00 | 4.29 |
| 0 | Singlet OPS | 0 | 0.03 | 1.97 | 5.14α/5.11β | 0.36 | 3.94 | 5.11α/4.82β | 0.01 | 3.64 | 5.03α/5.22β |
| 1 | Triplet | 2 | 0.21 | 2.95 | 4.73α/5.03β | 0.35 | 4.78 | 4.94α/5.39β | 0.00 | 4.70 | 5.31α/5.11β |
| 2 | Quintet | 4 | 0.00 | 6.05 | 7.29α/5.15β | 0.00 | 7.42 | 5.38α/5.02β | 0.05 | 7.60 | 5.31α/5.14β |
| 3 | Septet | 6 | 2.10 | 12.05 | 5.92α/5.42β | 0.32 | 12.77 | 5.29α/5.11β | 0.46 | 13.04 | 5.22α/5.12β |
| 4 | Nonet | 8 | 4.77 | 20.07 | 6.00α/5.22β | 0.69 | 20.05 | 5.29α/6.89β | 0.48 | 20.08 | 5.23α/6.85β |
| E eb | −7.04, −6.94a (−6.52) | −6.62, −6.23a (−6.23) | −5.78, −5.56a (−5.10) | ||||||||
a
Values of zero point corrected relative energy E0 in eV.