Table 4.
TD-ωb97xd-PCM/6-31G(3df,p) calculated vertical lowest lying transition energies (ΔE) in eV, and oscillator strength (f) of G(N1-H)•-(N4-H+)C. Structure is shown in scheme 1(c). See Figure S4 in the supporting information for MOs involved in transitions.
| State | Transitiona | ΔE (eV) |
λ (nm) |
f | Contribution | Red-shift 40 nm | Exp. (nm)c |
|
|---|---|---|---|---|---|---|---|---|
| ΔE (eV) | λ (nm) | |||||||
| D1 | GC(n)→G(π*)b | 1.95 | 637 | 0.0002 | 92% | 1.83 | 677 | |
| D2 | G(π)→G(π*) | 2.18 | 569 | 0.0104 | 84% | 2.04 | 609 | 550 – 650 |
| D3 | G(n)→G(π*) | 2.68 | 462 | 0.0001 | 73% | 2.47 | 502 | |
| D4 | G(π)→G(π*) | 2.75 | 450 | 0.0280 | 87% | 2.53 | 490 | 500 |
| D5 | C(π)→C(π*) | 3.24 | 383 | 0.0001 | 88% | 2.93 | 423 | |
| D6 | C(π)→G(π*) | 3.26 | 380 | 0.0029 | 92% | 2.95 | 420 | |
| D7 | GC(n)→C(π*)b | 3.47 | 357 | 0.0000 | 91% | 3.12 | 397 | |
| D8 | G(π)→G(π*) | 3.63 | 342 | 0.1158 | 89% | 3.25 | 382 | 380 |
| D9 | G(n)→G(π*) | 4.36 | 285 | 0.0001 | 71% | 3.82 | 325 | |
| D10 | C(π)→G(π*) | 4.39 | 282 | 0.0005 | 91% | 3.85 | 322 | |
| D11 | GC(n)→G(π*) | 4.53 | 274 | 0.0000 | 97% | 3.95 | 314 | |
| D12 | G(π)→G(π*) | 4.55 | 273 | 0.1703 | 79% | 3.96 | 313 | |
a
Nature (D1= LE, CT; D2= LE; D3=LE; D4=LE; D5=LE; D6=CT; D7=LE, CT; D8= LE; D9= LE; D10= CT; D11= LE, CT; D12= LE). LE = Local excitation; CT = charge transfer.
b
Delocalized on G and C.
c
See figure 5 in reference 21.