Table 2. Glyoxal VMC and DMC Total Energies (a.u.) and Excitation Energies (eV)a.
| VMC |
DMC |
|||||||
|---|---|---|---|---|---|---|---|---|
| WF | # det | # parm | E(11Ag) | E(21Ag) | ΔE | E(11Ag) | E(21Ag) | ΔE |
| CIPSI | 3749 | 2908 | –44.6072(2) | –44.3957(2) | 5.76(1) | –44.6564(2) | –44.4482(2) | 5.67(1) |
| 5046 | 3498 | –44.6127(2) | –44.4004(2) | 5.78(1) | –44.6600(2) | –44.4509(2) | 5.69(1) | |
| 7040 | 4500 | –44.6150(2) | –44.4048(2) | 5.72(1) | –44.6613(2) | –44.4534(2) | 5.66(1) | |
| 8642 | 5433 | –44.6181(2) | –44.4098(2) | 5.67(1) | –44.6632(2) | –44.4559(2) | 5.64(1) | |
| 10,010 | 6188 | –44.6205(2) | –44.4114(2) | 5.69(1) | –44.6635(2) | –44.4567(2) | 5.63(1) | |
| 12,132 | 6269 | –44.6237(2) | –44.4145(2) | 5.70(1) | –44.6654(2) | –44.4576(2) | 5.66(1) | |
| 15,349 | 8577 | –44.6276(2) | –44.4180(2) | 5.70(1) | –44.6670(2) | –44.4600(2) | 5.63(1) | |
| TBEb | 5.61 | |||||||
| CC3/AVQZc | 6.76 | |||||||
| CC4/6-31+G*d | 5.699 | |||||||
| CC4/AVDZd | 5.593 | |||||||
| CCSDTQ/6-31+G*d | 5.670 | |||||||
| exFCI/AVDZ | 5.56(11) | |||||||
| SAC-CI/AVDZe | 5.66 | |||||||
| CASPT2(14,12)/AVQZc | 5.43 | |||||||
| PC-NEVPT2(14,12)/AVQZc | 5.52 | |||||||
a
The number of determinants (# det) and parameters (# parm) in each trial wave function are also presented. The CIPSI expansions are performed on a NO basis and fully reoptimized in VMC.
b
This value is “safe”, as defined in ref (12), exFCI/AVDZ + (CCSDT/AVTZ-CCSDT/AVDZ).
c
Ref (13).
d
Ref (16).
e
Ref (61), see reference for basis set details.