Table 1. Charge Contributions to the β spin Molecular Orbitals of the Cyt P450cam active site model (cf. Scheme 1) calculated with BP86/TZVP.
| No. | Labela | Energy/Hartree | Fe, d | S, p | Porphyrin |
|---|---|---|---|---|---|
| β<228> | πsc(cp) + π/σsc(por) | -0.03146 | 0 | 0 | 2 |
| β<227> | πsc(por)+B1u | -0.03898 | 1 | 0 | 34 |
| β<226> | π/σsc(por) | -0.04348 | 0 | 0 | 2 |
| β<225> | πsc(por) | -0.04681 | 0 | 0 | 0 |
| β<224> | πsc(por) | -0.04704 | 0 | 0 | 0 |
| β<223> | B1u<84> | -0.06886 | 2 | 0 | 72 |
| β<222> | dx2-y2_ B1g<80> | -0.08264 | 61 | 0 | 32 |
| β<221> | dz2_S(pz)+A2u<81> | -0.10842 | 56 | 17 | 14 |
| β<220> | Eg<82/83>_dyz | -0.11245 | 12 | 0 | 77 |
| β<219> | Eg<82/83>_dxz+S(px) | -0.11598 | 15 | 1 | 71 |
| β<218> | dxz_S(px) | -0.13665 | 55 | 19 | 18 |
| β<217> | dyz | -0.15322 | 68 | 1 | 22 |
| β<216> | dxy (LUMO) | -0.15777 | 93 | 0 | 4 |
| β<215> | π/σsc(cp) (HOMO) | -0.18567 | 0 | 0 | 0 |
| β<214> | A1u<79> | -0.19331 | 0 | 0 | 89 |
| β<213> | π/σsc(cp) | -0.19560 | 0 | 1 | 1 |
| β<212> | A2u<81>_dz2 + S(px) | -0.20275 | 4 | 7 | 82 |
| β<211> | S(px)_dxz | -0.20470 | 9 | 36 | 39 |
| β<210> | πsc(cp) | -0.21646 | 1 | 2 | 1 |
| β<209> | πsc(cp) | -0.21693 | 1 | 1 | 1 |
| β<208> | B2u<74>+S(px) | -0.22086 | 1 | 2 | 51 |
| β<207> | π/σsc(por)+πpor | -0.22569 | 3 | 3 | 31 |
| β<206> | A1u(dis)+S(py) + πsc(cp,por) | -0.22943 | 4 | 6 | 46 |
| β<205> | πsc(cp) + πpor+S(px)+σsc(por) | -0.23415 | 3 | 10 | 22 |
| β<204> | πsc(cp) + πpor + dz2 | -0.23693 | 8 | 5 | 27 |
| β<203> | πpor+πsc(por) | -0.24000 | 3 | 2 | 47 |
| β<202> | πpor+π/σsc(por) | -0.24530 | 3 | 1 | 44 |
| β<201> | S(pz)_dz2 | -0.24839 | 15 | 38 | 1 |
| β<200> | π/σsc(cp) | -0.24944 | 1 | 3 | 2 |
| β<199> | πsc(por) | -0.25893 | 1 | 0 | 11 |
| β<198> | Eg<59/60> | -0.26373 | 1 | 1 | 80 |
| β<197> | Eg<59/60> | -0.26706 | 0 | 0 | 90 |
| β<196> | Eu(σ) | -0.28341 | 6 | 0 | 89 |
| β<195> | A1u(dis)+πsc(por) | -0.28439 | 2 | 0 | 52 |
| β<194> | πsc(por) | -0.28804 | 0 | 0 | 5 |
| β<193> | Eu(σ)_dx2y2 | -0.29459 | 10 | 2 | 62 |
| β<192> | σpor_dx2-y2 | -0.29840 | 11 | 0 | 60 |
| β<191> | π/σsc(por)+πpor | -0.30347 | 0 | 0 | 24 |
| β<190> | π/σsc(por)+πpor + S(py) | -0.30480 | 2 | 2 | 27 |
| β<189> | B2u(dis)+S(py) + π/σsc(cp) | -0.30572 | 3 | 8 | 38 |
| β<188> | B1u+πsc(por) + S(py) | -0.31095 | 1 | 2 | 46 |
| β<187> | B1u+πsc(por,cp) + S(py) | -0.31186 | 1 | 5 | 42 |
| β<186> | πsc(cp)+S(px/y)_dz2 | -0.31519 | 2 | 6 | 3 |
a
Abbreviations: sc – side chain, cp – Cys pocket, por – porphyrin, dis – distorted, S(px/y) – electron densities are in between the x and y axis. S(px), S(py) and S(pz) are the sulfur 3p orbitals.