Table 3. LVC Energies (eV) of the Diabatic (EiiD[Dmin]) and Adiabatic (Em[Dmin]) States of AT at the Diabatic State Minima (Dmin) Predicted by the Different LVC Models and Selected TD-DFT Adiabatic Energies at the TD-DFT Predicted Adiabatic Minima EmA,DFT[Amin]a.
| St-LVC |
FrD(MMref)-LVC |
FrD-LVC |
TD-DFT | |||||
|---|---|---|---|---|---|---|---|---|
| ad. state m/diab state i | character | EiiD[Dmin] | EmA,LVC[Dmin] | EiiD[Dmin] | EmA,LVC[Dmin] | EiiD[Dmin] | EmA,LVC[Dmin] | EmA,DFT[Amin] |
| 1 | T(ππ*1) | 4.99 | 4.98 (0.98) | 4.99 | 4.99 (0.99) | 5.00 | 5.00 (0.99) | 4.99 |
| 2 | T(nOπ*1) | 4.97 | 4.96 (0.99) | 4.96 | 4.96 (0.99) | 4.97 | 4.97 (0.99) | 4.85 |
| 3 | A(La) | 5.16 | 5.11 (0.94) | 5.17 | 5.12 (0.94) | 5.19 | 5.14 (0.93) | 5.08 |
| 4 | A(Lb) | 5.33 | 5.27 (0.67) | 5.33 | 5.29 (0.67) | 5.36 | 5.30 (0.56) | |
| 5 | A(nNπ*1) | 5.08 | 5.06 (0.98) | 5.12 | 5.10 (0.98) | 5.21 | 5.19 (0.98) | 4.99 |
| 6 | A → T (CT) | 5.00 | 4.93 (0.95) | 4.99 | 4.99 (0.99) | 5.01 | 5.01 (0.99) | 4.82 |
| 7 | A(nNπ*2) | 5.66 | 5.73 (0.58) | 5.65 | 5.73 (0.54) | 5.74 | 5.80 (0.62) | |
| 8 | T(nOπ*2) | 5.86 | 5.90 (0.64) | 5.86 | 5.80 (0.55) | 5.89 | 5.94 (0.62) | |
| 9 | A(nNπ*3) | 6.24 | 6.23 (0.80) | 6.25 | 6.25 (0.84) | 6.23 | 6.25 (0.96) | |
| 10 | T(ππ*2) | 6.14 | 5.99 (0.57) | 5.96 | 5.96 (0.98) | 5.97 | 5.94 (0.97) | |
| 11 | T(ππ*3) | 6.34 | 6.21 (0.87) | 6.20 | 6.19 (0.99) | 6.22 | 6.20 (0.98) | |
| 12 | A(ππ*3) | 6.70 | 6.75 (0.47) | 6.61 | 6.62 (0.99) | 6.62 | 6.62 (0.99) | |
a
Values in parentheses give the weight of the corresponding diabatic state in the adiabatic state. LVC models are parameterized with CAM-B3LYP/6-31G(d) calculations.