Table 5.
DFT-computed relative energies and compositions (%) of the occupied azide πnb- and unoccupied Fe3+ 3d-based spin-down MOs for the QM/MM optimized active-site models of Q69E N3-Fe3+SOD, N3-Fe3+SOD, N3-Fe3+(Mn)SOD, and Y34F N3-Fe3+(Mn)SOD
| Fe 3d orbitals |
Azide πnb |
|||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| MOa | E (eV)b | occc | xy | yz | xz | x2-y2 | z2 | px | py | pz |
| Q69E N3-Fe3+SOD | ||||||||||
| Fe 3dz2 | 4.606 | 0 | 0 | 0 | 0 | 8 | 62 | 2 | 0 | 2 |
| Fe 3dx2-y2 | 4.419 | 0 | 0 | 1 | 14 | 53 | 4 | 2 | 1 | 1 |
| Fe 3dxz | 3.371 | 0 | 5 | 0 | 62 | 16 | 1 | 0 | 5 | 0 |
| Fe 3dyz | 3.331 | 0 | 1 | 82 | 0 | 1 | 0 | 0 | 0 | 1 |
| Fe 3dxy | 3.263 | 0 | 79 | 1 | 3 | 2 | 1 | 0 | 0 | 1 |
| N3− πnb(op) | 0.235 | 1 | 0 | 0 | 3 | 1 | 0 | 1 | 20 | 9 |
| N3− πnb(ip) | 0 | 1 | 0 | 0 | 2 | 1 | 2 | 11 | 8 | 11 |
| N3-Fe3+SOD | ||||||||||
| Fe 3dz2 | 4.954 | 0 | 0 | 0 | 22 | 1 | 43 | 0 | 0 | 0 |
| Fe 3dx2-y2 | 4.516 | 0 | 22 | 2 | 5 | 41 | 1 | 2 | 0 | 0 |
| Fe 3dxz | 3.644 | 0 | 2 | 9 | 41 | 7 | 27 | 0 | 0 | 1 |
| Fe 3dxy/dyz | 3.551 | 0 | 30 | 33 | 2 | 11 | 4 | 0 | 0 | 0 |
| Fe 3dxy/dyz | 3.427 | 0 | 28 | 36 | 6 | 16 | 2 | 0 | 0 | 0 |
| N3− πnb(op) | 0.292 | 1 | 0 | 0 | 2 | 1 | 1 | 3 | 4 | 40 |
| N3− πnb(ip) | 0 | 1 | 0 | 0 | 1 | 4 | 0 | 12 | 33 | 1 |
| N3-Fe3+(Mn)SOD | ||||||||||
| Fe 3dz2 | 5.234 | 0 | 0 | 0 | 0 | 17 | 50 | 0 | 0 | 0 |
| Fe 3dx2-y2 | 4.627 | 0 | 3 | 0 | 0 | 56 | 13 | 1 | 0 | 0 |
| Fe 3dxz | 3.831 | 0 | 0 | 2 | 86 | 0 | 1 | 0 | 0 | 0 |
| Fe 3dyz | 3.736 | 0 | 7 | 67 | 3 | 1 | 0 | 0 | 0 | 0 |
| Fe 3dxy | 3.63 | 0 | 75 | 8 | 0 | 2 | 1 | 0 | 0 | 0 |
| N3− πnb(op) | 0.268 | 1 | 1 | 0 | 1 | 0 | 0 | 0 | 23 | 16 |
| N3− πnb(ip) | 0 | 1 | 1 | 0 | 0 | 1 | 2 | 28 | 4 | 9 |
| Y34F N3-Fe3+(Mn)SOD | ||||||||||
| Fe 3dz2 | 5.134 | 0 | 0 | 1 | 0 | 8 | 57 | 0 | 0 | 0 |
| Fe 3dx2-y2 | 4.564 | 0 | 1 | 1 | 0 | 66 | 7 | 1 | 0 | 0 |
| Fe 3dxz | 3.757 | 0 | 0 | 4 | 83 | 0 | 1 | 0 | 0 | 1 |
| Fe 3dyz | 3.633 | 0 | 6 | 68 | 5 | 2 | 0 | 0 | 0 | 0 |
| Fe 3dxy | 3.523 | 0 | 78 | 6 | 0 | 1 | 1 | 1 | 1 | 0 |
| N3− πnb(op) | 0.373 | 1 | 2 | 0 | 2 | 0 | 0 | 0 | 29 | 16 |
| N3− πnb(ip) | 0 | 1 | 0 | 2 | 0 | 1 | 1 | 26 | 4 | 11 |
a
MOs are labeled according to their principal orbital contributors.
b
All MO energies are given relative to the energy of the corresponding πnb(ip)-based MO.
c
MO occupancies.