Table 5. Energies E (eV), Wavelengths λ (nm), and Oscillator Strengths f of the Main (f ≥ 0.005) UV–vis–NIR Electronic Transitions Calculated for 3 in the Gas Phase and in CH2Cl2 and CHCl3 at the IEF-PCM TD-RDFT Levela.
| gas phase |
CHCl3 |
CH2Cl2 |
|||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| ESb | symm | E | λ | f | E | λ | f | E | λ | f | main contribution |
| 1 | 1A1 | 1.489 | 832.6 | 0.315 | 1.415 | 876.0 | 0.385 | 1.436 | 863.8 | 0.368 | H(93) → L(94) (100%) |
| 7 | 1A1 | 2.931 | 423.0 | 0.153 | 2.950 | 420.3 | 0.303 | 2.974 | 416.9 | 0.324 | H-3(90) → L(94) (91%) |
| 9 | 1B2 | 2.983 | 415.7 | 0.009 | 2.962 | 418.6 | 0.011 | 2.966 | 418.0 | 0.008 | H-5(88) → L(94) (92%) |
| 13 | 1A1 | 3.586 | 345.8 | 0.096 | 3.691 | 335.9 | 0.121 | 3.719 | 333.4 | 0.122 | H-8(85) → L(94) (91%) |
| 15 | 1B2 | 3.787 | 327.4 | 0.046 | 3.616 | 342.9 | 0.076 | 3.583 | 346.1 | 0.076 | H-7(86) → L+1(95 (15%), H(93) → L+2(96) (75%) |
| 17 | 1A1 | 4.133 | 300.1 | 0.121 | 4.135 | 299.9 | 0.240 | 4.132 | 300.1 | 0.250 | H-2(91) → L+1(95) (96%) |
| 20 | 1B2 | 4.364 | 284.2 | 0.005 | 4.294 | 288.8 | 0.007 | 4.274 | 290.1 | 0.006 | H-13(80) → L+1(95) (19%), H-9(84) → L+1(95) (65%) |
a
KS-HOMO (H) = MO 93; KS-LUMO (L) = MO 94.
b
Excited state (ES) numbering taken from gas-phase calculations.