Table 2.
Electronic Transitions for ZnF16Pc, ZnF12(SR)4Pc-β, ZnF8(SR)8Pc-β, ZnF4(SR)12Pc-β, and Zn(SR)16Pc, Calculated by TD-DFT Using the B3LYP Hybrid Exchange—Correlation Functional and the 6–31G(d,p) Basis Seta
| compound | λb | f c | wave functiond |
|---|---|---|---|
| ZnF16Pc | 616 | 0.442 | 95% (H → L) + … |
| 613 | 0.444 | 95% (H→ L+1) + … | |
| 367 | 0.107 | 5% (H−9 → L+1) + 30% (H−5 → L+1) + 63% (H−3 → L) + … | |
| 366 | 0.144 | 6% (H−9 → L) + 21% (H−5 → L) + 67% (H−3 → L+1) + … | |
| ZnF12(SR)4Pc−β | 644 | 0.562 | 96% (H → L) + … |
| 641 | 0.586 | 96% (H → L+1) + … | |
| 441 | 0.110 | 88% (H−4 → L) + 7% (H−2 → L) + … | |
| 436 | 0.119 | 94% (H−4 → L+1) + … | |
| 383 | 0.164 | 93% (H−6 → L) + … | |
| 382 | 0.155 | 93% (H−6 → L+1) + … | |
| ZnF8(SR)8Pc−β | 674 | 0.608 | 96% (H → L) + … |
| 661 | 0.641 | 95% (H → L+1) + … | |
| 354 | 0.187 | 6% (H−18 → L) + 36% (H−14 → L) + 25% (H−13→L) + 14% (H−13 → L+1) + 6% (H−12 → L+1) + … | |
| 351 | 0.108 | 10% (H−13 → L) + 31% (H−13 → L+1) + 13% (H−12 → L) + 29% (H−12 → L+1) + … | |
| ZnF4(SR)12Pc−β | 705 | 0.492 | 95% (H → L) + … |
| 698 | 0.542 | 95% (H → L+1) + … | |
| Zn(SR)16Pc | 700 | 0.476 | 93% (H → L) + … |
| 688 | 0.522 | 92% (H → L+1) + … |
A more complete table of transitions is given in the Supporting Information (Table S2).
Transition wavelengths in nanometers. Only transitions with energies below ∼3.5 eV (>350 nm) are given.
Calculated oscillator strengths. Only transitions with oscillator strengths greater than 0.10 are given.
Excited-state wave function, in terms of the contributions of single excitations of the ground-state Slater determinant. Only single excitations with contributions greater than 5% are given. The HOMO is designated “H”, the second HOMO is “H−1″, etc. The LUMO is designated “L”, the second LUMO is “L+1”, etc. Excitations involving only orbitals corresponding to Gouterman’s four-orbital model are shown in italics.