Table 1. Calculated Dominant Vertical Excitation Energies (TD-DFT/B3LYP/aug-cc-pVDZ) and Oscillator Strengths of CH3NO2, Compared Where Possible with the Corresponding Experimental Data and Other Work in the Literature (Energies in eV)a.
| nitromethane
(CH3NO2) |
|||||||
|---|---|---|---|---|---|---|---|
| state | E (eV) | fL | dominant excitations | Eexp. (eV)b | cross-section (Mb) | E (eV)1 | E (eV)3 |
| X̃ 1A′ | |||||||
| 2 1A″ | 4.605 | 0.00002 | π*(4a″) ← n̅O/σCN(12a′) (100%) | 4.550 | 0.04 | 4.5 | |
| 2 1A′ | 6.879 | 0.15459 | π*(4a″) ← π(3a″) (90%) | 6.271 | 17.74 | 6.25 | 6.27 |
| 3 1A′ | 7.100 | 0.00037 | 3s(14a′) ← n̅O(13a′) (95%) | 7.637 | 2.59 | 7.44 | 7.531 |
| 4 1A′ | 7.510 | 0.03627 | 3s(14a′) ← n̅O/σCN(12a′) (97%) | 8.38(3)(s) | 12.13 | 8.07 | 8.257 |
| 6 1A′ | 8.223 | 0.02625 | 3px/σ(16a′) ← n̅O(13a′) (72%) + 3py(15a′) ← n̅O(13a′) (22%) | 7.92(5) | 5.98 | 7.8 | 7.974 |
| 9 1A′ | 8.851 | 0.10584 | π*(4a″) ← πNO(2a″) (70%) + 3px/σ(16a′) ← n̅O/σCN(12a′) (21%) | 8.803 | 16.33 | 8.3 | 8.531 |
| 12 1A′ | 9.702 | 0.20343 | σCN*(17a′) ← n̅O/σCN(12a′) (79%) + 4s/4py(19a′) ← n̅O(13a′) (14%) | 9.450 | 27.35 | 9.368 | |
| 19 1A′ | 10.696 | 0.03473 | 4s/5pz(20a′) ← n̅O/σCN(12a′) (93%) | 10.315 | 23.63 | 10.347 | |
| 18 1A″ | 10.960 | 0.02397 | 4s/π*(20a′) ← n̅O/σCN(12a′) (90%) | 10.739 | 22.32 | 10.798 | |
a
See text for details.
b
The last decimal of the energy value is given in parentheses for these less-resolved features.