Table 5.
TD-ωb97xd-PCM/6-31G(3df,p) calculated vertical lowest lying transition energies (ΔE) in eV, and oscillator strength (f) of G(N1-H)•-C. Structure is shown in scheme 1(d). See Figure S5 in the supporting information for MOs involved in transitions.
| State | Transitiona | ΔE (eV) |
λ (nm) |
f | Contribution | Red-shift 40 nm | |
|---|---|---|---|---|---|---|---|
| ΔE (eV) | λ (nm) | ||||||
| D1 | G(n)→G(π*)b | 1.92 | 644 | 0.0003 | 90% | 1.81 | 684 |
| D2 | GC(π)→G(π*)c | 2.09 | 592 | 0.0266 | 91% | 1.96 | 632 |
| D3 | GC(n)→G(π*)c | 2.65 | 469 | 0.0001 | 88% | 2.44 | 509 |
| D4 | G(π)→G(π*) | 2.73 | 455 | 0.0576 | 91% | 2.51 | 495 |
| D5 | GC(n)→G(π*)b | 3.43 | 362 | 0.0000 | 80% | 3.08 | 402 |
| D6 | G(π)→G(π*) | 3.57 | 347 | 0.1849 | 91% | 3.20 | 387 |
| D7 | C(π)→C(π*) | 3.65 | 340 | 0.0000 | 90% | 3.26 | 380 |
| D8 | C(π)→G(π*) | 3.84 | 323 | 0.0004 | 75% | 3.42 | 363 |
| D9 | GC(π)→G(π*)c | 4.04 | 307 | 0.0003 | 99% | 3.57 | 347 |
| D10 | G(n)→G(π*) | 4.30 | 288 | 0.0002 | 70% | 3.78 | 328 |
| D11 | G(π)→G(π*) | 4.50 | 276 | 0.2149 | 83% | 3.92 | 316 |
| D12 | C(π)→C(π*) | 4.52 | 274 | 0.0003 | 61% | 3.95 | 314 |
a
Nature (D1= LE; D2= LE, CT; D3=LE, CT; D4=LE; D5=LE; D6=LE; D7=LE; D8= CT; D9= LE, CT; D10= LE; D11= LE; D12= LE). LE = Local excitation; CT = charge transfer.
b
Very small mixing with cytosine.
c
Delocalized on G and C.