Table 3. RCCSD(T)-F12/AVTZ relative energies (E, E ZPVE, in cm -1), internal rotation barriers (V 3, V 2, in cm -1).
Rotational constants (in MHZ), MRCI/CASSCF/AVTZ dipole moment (in D) and equilibrium structural parameters ( distances, in Å, angles, in degrees) of acetyl, vinoxy, and 1-methylvinoxy radicals.
| CH
3CO
a
(X 2A’) |
CH
2CHO
(X 2A”) |
CH
3COCH
2
b
(X 2A”) |
|
|---|---|---|---|
| E | 0.0 | 2514.2 | - |
| E ZPVE | 0.0 | 2498.8 | - |
| V 2 | - | 3838.7 | 2727.5 |
| V 3 | 143.7 | - | 161.4 |
| A e | 84134.35 | 67084.88 | 10934.76 |
| B e | 9982.57 | 11456.25 | 9115.74 |
| C e | 9444.29 | 9785.20 | 5128.93 |
| μ a | 0.2423 | 0.9465 | 0.5444 |
| μ b | 2.3244 | 2.6175 | 1.3272 |
| μ c | 0.0 | 0.0 | 0.0 |
| μ | 2.3281 | 2.7834 | 1.4346 |
| CH 3CO | CH 2CHO | ||
| C1C2 | 1.5116 | C1C2 | 1.4325 |
| O3C1 | 1.1816 | O3C2 | 1.2290 |
| H4C2 | 1.0912 | H4C2 | 1.1014 |
| H5C2=H6C2 | 1.0892 | H5C1=H6C1 | 1.0809 |
| O3C1C2 | 128.3 | O3C2C1 | 122.8 |
| H4C2C1 | 110.7 | H4C2C1 | 117.0 |
| H5C2C1=H6C2C1 | 108.4 | H5C1C2 | 119.0 |
| H4C2C1O3 | 0.0 | H6C1C2 | 120.9 |
| H5C2C1H4=-H6C2C1H4 | 121.6 | ||
| CH 3COCH 2 | |||
| C1C2 | 1.5129 | C2C1O4 | 121.6 |
| C1C3 | 1.4467 | H5C2C1 | 109.5 |
| O4C1 | 1.2291 | H6C2C1=H7C2C1 | 110.2 |
| H5C2 | 1.0869 | C1C3H8 | 118.1 |
| H6C2=H7C2 | 1.0917 | H9C3H8 | 119.9 |
| H8C3 | 1.0803 | H5C2C1C3 | 180.0 |
| H9C3 | 1.0814 | H6C2C1H5=
-H7C2C1H5 |
120.8 |
| C2C1C3 | 117.9 | ||
| a) E=-152.989163 a.u.; b) E=-192.240093 a.u. | |||