Table 3. Computed Franck–Condon Excitation Energies (in eV) and Oscillator Strengths in the Adiabatic and Pseudo-diabatic Basisa.
| benzene |
toluene |
aniline |
fluorobenzene |
phenol |
||||||
|---|---|---|---|---|---|---|---|---|---|---|
| method | ΔE | f | ΔE | f | ΔE | f | ΔE | f | ΔE | f |
| Adiabatic | ||||||||||
| MRCI | 5.08 | 0.0000 | 4.98 | 0.0000 | 4.83 | 0.0074 | 5.08 | 0.0025 | 4.96 | 0.0070 |
| XMS-CASPT2 | 4.89 | 0.0000 | 4.76 | 0.0001 | 4.53 | 0.0080 | 4.86 | 0.0025 | 4.59 | 0.0531 |
| EOM-CCSD | 5.18 | 0.0000 | 5.12 | 0.0011 | 4.78 | 0.0384 | 5.24 | 0.0097 | 5.07 | 0.0234 |
| ADC(2) | 5.25 | 0.0000 | 5.16 | 0.0013 | 4.71 | 0.0464 | 5.26 | 0.0152 | 5.04 | 0.0323 |
| ADC(3) | 4.98 | 0.0000 | 4.91 | 0.0013 | 4.59 | 0.0389 | 5.05 | 0.0092 | 4.89 | 0.0227 |
| B3LYP | 5.50 | 0.0000 | 5.31 | 0.0017 | 4.80 | 0.0501 | 5.43 | 0.0133 | 5.20 | 0.0330 |
| CAM-B3LYP | 5.66 | 0.0000 | 5.43 | 0.0021 | 5.04 | 0.0561 | 5.60 | 0.0147 | 5.39 | 0.0359 |
| M06-2X | 5.71 | 0.0000 | 5.51 | 0.0021 | 5.10 | 0.0573 | 5.67 | 0.0153 | 5.47 | 0.0361 |
| ωB97X | 5.69 | 0.0000 | 5.49 | 0.0022 | 5.12 | 0.0576 | 5.63 | 0.0155 | 5.44 | 0.0369 |
| Diabatic | ||||||||||
| MRCI | 5.05 | 0.0029 | 5.47 | 0.0066 | 4.84 | 0.0033 | 5.45 | 0.0042 | 5.01 | 0.0080 |
| XMS-CASPT2 | 4.91 | 0.0048 | 5.21 | 0.0097 | 4.80 | 0.0044 | 5.38 | 0.0074 | 4.99 | 0.0118 |
| Expt. | 4.88 | 0.0006 | 4.62 | 0.0050 | 3.69 | 0.0355 | 4.73 | 0.0076 | 4.56 | 0.0161 |
a
Experimental data taken from ref (62).