Table 2.
Ni(3d), S(3p), and N(2p) Löwdin MO population analysis (%AO to MO) and energies (E, eV) relative to the HOMO for the LUMO+1 through HOMO-5 of the computational model for the disulfide bridged dinuclear {Ni2(SODmds)} nickel site computational model. Orbital compositions for the doubly-protonated model are given above the unprotonated model for each AO.
| LUMO+1 | LUMO | HOMO | HOMO-1 | HOMO-2 | HOMO-3 | HOMO-4 | HOMO-5 | |
|---|---|---|---|---|---|---|---|---|
| Ni1 | 0.3 | 21.1 | 28.2 | 4.8 | 11.8 | 20.3 | 7.5 | 18.5 |
| Ni2 | 50.6 | 0.4 | 4.3 | 23.3 | 11.7 | 1.7 | 24.6 | 38.4 |
| S3 | 0.4 | 16.4 | 10.4 | 1.5 | 1.2 | 10.2 | 0.1 | 0.4 |
| S4 | 0.4 | 17.1 | 5.2 | 0.2 | 0.6 | 88 | 0.8 | 7.3 |
| S5 | 6.1 | 2.0 | 4.2 | 2.0 | 9.5 | 0.6 | 1.2 | 1.1 |
| S6 | 8.7 | 2.4 | 9.5 | 1.4 | 8.9 | 0.4 | 6.0 | 1.4 |
| S7 | 0.1 | 5.1 | 21.9 | 4.6 | 15.6 | 30.0 | 6.1 | 5.1 |
| S8 | 10.1 | 0.0 | 3.2 | 49.2 | 15.2 | 0.4 | 2.3 | 4.3 |
| N9 | 0.2 | 1.6 | 0.4 | 0.2 | 1.7 | 6.1 | 5.7 | 5.5 |
| N10 | 3.0 | 0.0 | 0.2 | 0.9 | 5.0 | 0.8 | 14.9 | 3.8 |
| E | 3.76 | 3.62 | 0.00 | –0.30 | –0.54 | –0.69 | –0.72 | –1.07 |
1
more distorted nickel site
2
less distorted nickel site
3
disulfide sulfur over Ni1
4
disulfide sulfur over Ni2
5
bridging thiolate sulfur
6
bridging thiolate sulfur
7
terminal thiolate sulfur ligated to Ni1
8
terminal thiolate ligated to Ni2
9
amidate nitrogen ligated to Ni1
10
amidate nitrogen ligated to Ni2.