Table 2. MRCIS(8,7)+P/ANO-DZ Vertical (vert) Absorption and Fluorescence (fl) Energies (eV) and Minimum-to-Minimum (m-m) Energies in the Gas Phase and in AN Solution of Optimized Ground-State, LE, and CT structures of DMABN.
| gas
phase |
AN |
||||
|---|---|---|---|---|---|
| structure (symmetry) | state | calcda | exptlb | calcdnoneq | exptlc |
| gr. state (C2v) | vert. 11B2 (ππ*) | 4.32 (0.025) | 4.13 | 4.34 | 3.86 |
| vert. 21A1 (ππ*) | 4.90 (0.688) | 4.57 | 4.75 | 4.24 | |
| LE state (C2) | Ted 11B (ππ*) | 4.13 | 4.15 | ||
| ν00 11B (ππ*) | (3.95)e | 3.998f | |||
| fl 11B (ππ*) | 3.93 (0.012) | 3.68 | 3.94 | 3.44 | |
| CT state (C1) | Ted 21A (ππ*) | 4.29 | 3.90 | ||
| fl 21A (ππ*) | 3.27 (0.004) | 3.55 (extrap.) | 2.77 | 2.52 | |
a
Oscillator strengths (absorption) are given in parentheses.
b
Ref (43).
d
Adiabatic excitation energy (rel to the ground-state minimum).
e
Position of 0–0 transition (approximation); the result in ref (27) was used. ν00 energy is about 0.2 eV below Te energy for LE state.
f
Laser-induced fluorescence (LIF) excitation spectrum in the gas phase, ref (45).