Table 3. Absolute Value of the Qy Excitation Energy (with the Electrostatic Embedding Using the QM/MM Optimized Structure) Using Various Quantum Chemical Methodsa.
| method | PD1 | PD2 | ChlD1 | ChlD2 | PheoD1 | PheoD2 |
|---|---|---|---|---|---|---|
| DLPNO-STEOM-CCSD | 1.613 (0.27) | 1.620 (0.26) | 1.575 (0.30) | 1.624 (0.26) | 1.743 (0.13) | 1.768 (0.12) |
| CC2 | 2.137 (0.25) | 2.134 (0.20) | 2.098 (0.27) | 2.105 (0.25) | 2.114 (0.19) | 2.099 (0.18) |
| ADC (2) | 1.920 (0.28) | 1.918 (0.25) | 1.878 (0.29) | 1.874 (0.29) | 1.916 (0.23) | 1.897 (0.22) |
| SCS-CC2 | 2.051(0.27) | 2.058 (0.24) | 2.011 (0.30) | 2.046 (0.27) | 2.134 (0.17) | 2.142 (0.17) |
| SCS-ADC(2) | 1.940 (0.31) | 1.947 (0.29) | 1.898 (0.35) | 1.930 (0.31) | 2.059 (0.19) | 2.070 (0.20) |
| SOS-CC2 | 2.004 (0.26) | 2.012 (0.24) | 1.961 (0.29) | 2.010 (0.25) | 2.154 (0.14) | 2.171 (0.14) |
| SOS-ADC(2) | 1.924 (0.29) | 1.933 (0.27) | 1.879 (0.33) | 1.926 (0.28) | 2.098 (0.16) | 2.116 (0.15) |
| ωΒ97 | 1.835 (0.25) | 1.829 (0.24) | 1.781 (0.28) | 1.852 (0.24) | 2.026 (0.15) | 2.040 (0.15) |
| ωΒ97X-V | 1.907 (0.26) | 1.904 (0.24) | 1.856 (0.29) | 1.916 (0.26) | 2.064 (0.17) | 2.075 (0.17) |
| ωB2PLYP | 1.881 (0.28) | 1.881 (0.27) | 1.833 (0.32) | 1.885 (0.27) | 2.025 (0.17) | 2.040 (0.17) |
| LC-BLYP | 1.874 (0.24) | 1.868 (0.23) | 1.824 (0.27) | 1.882 (0.24) | 2.017 (0.15) | 2.027 (0.15) |
| CAM-B3LYP | 2.000 (0.27) | 2.001 (0.25) | 1.958 (0.31) | 2.000 (0.27) | 2.093 (0.20) | 2.098 (0.20) |
| CAM-B3LYP* | 2.050 (0.27) | 2.055 (0.24) | 2.012 (0.30) | 2.044 (0.27) | 2.104 (0.21) | 2.101 (0.21) |
| B2PLYP | 2.033 (0.31) | 2.043 (0.28) | 1.996 (0.34) | 2.018 (0.31) | 2.046 (0.22) | 2.047 (0.23) |
| BHandHLYP | 2.045 (0.31) | 2.048 (0.28) | 2.004 (0.34) | 2.046 (0.31) | 2.147 (0.23) | 2.151 (0.24) |
| B1LYP | 2.073 (0.28) | 2.080 (0.25) | 2.036 (0.31) | 2.065 (0.28) | 2.119 (0.22) | 2.114 (0.22) |
| B3LYP | 2.066 (0.27) | 2.073 (0.24) | 2.029 (0.29) | 2.057 (0.27) | 2.101 (0.21) | 2.094 (0.21) |
| PBE0 | 2.089 (0.28) | 2.096 (0.25) | 2.051 (0.31) | 2.081 (0.28) | 2.133 (0.22) | 2.129 (0.23) |
| PBE | 1.983 (0.12) | 1.997 (0.19) | 1.953b (0.24) | 1.974b (0.19) | 1.903 (0.10) | 1.883 (0.08) |
| BLYP | 1.970 (0.13) | 1.984 (0.19) | 1.941b (0.24) | 1.959 (0.11) | 1.895 (0.10) | 1.873 (0.08) |
| BP86 | 1.981 (0.13) | 1.996 (0.19) | 1.951b (0.24) | 1.971 (0.11) | 1.903 (0.10) | 1.882 (0.09) |
| ZINDO/S | 1.554 (0.38) | 1.563 (0.35) | 1.524 (0.39) | 1.571(0.36) | 1.747 (0.17) | 1.772 (0.16) |
The electronic excitation energies are reported in the electron volt units (eV) and the oscillator strengths corresponding to the excited state are shown in the parentheses.
These energies correspond to the second excited state (S2); the S1 state predicted in these cases is physically incorrect.