Table 1.
Observed and calculated geometric parameters of [Fe(OEP)(NO)].a
| [Fe(OEP)(NO)] | Geometric parameters (pm or degree)
|
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|---|---|---|---|---|---|---|---|---|---|---|---|
| Functional | Basis set | Fe-NO | ΔFe-NO | N-O | ΔN-O | □Fe-N-O | Δ□Fe-N-O | Fe-Nshorte | Fe-Nlonge | Δlong-short | Ref. |
| Triclinic crystal (experimental) | 173.1 | 116.8 | 142.7 | 199.9 | 202.0 | 2.1 | 12b | ||||
|
| |||||||||||
| BP86 | 6-31G*/VTZ | 169.7 | −3.4 | 119.2 | 2.4 | 143.2 | 0.5 | 200.3 | 203.1 | 2.8 | 12b |
| 6-31+G*(N,O)b/VTZ | 169.6 | −3.5 | 119.5 | 2.7 | 143.6 | 0.9 | 200.3 | 203.3 | 3.0 | f | |
| 6-31G*/TZVP | 169.6 | −3.5 | 119.1 | 2.3 | 144.9 | 2.2 | 200.9 | 203.9 | 3.0 | f | |
|
| |||||||||||
| MPWPW91 | 6-31G*/VTZ | 169.8 | −3.3 | 119.0 | 2.2 | 142.8 | 0.1 | 200.1 | 202.9 | 2.8 | f |
| 6-31+G*(N,O)b/VTZ | 169.6 | −3.5 | 119.3 | 2.5 | 143.7 | 1.0 | 200.3 | 203.3 | 3.0 | f | |
| 6-31G*/TZVP | 169.6 | −3.5 | 118.9 | 2.1 | 144.7 | 2.0 | 200.8 | 203.8 | 3.0 | f | |
|
| |||||||||||
| B3LYPd | 6-31G*/Lanl2DZ | 172.8 | −0.3 | 117.0 | 0.2 | 139.8 | −2.9 | 200.7 | 203.1 | 2.4 | f |
| Lanl2DZc | 174.2 | 1.1 | 121.5 | 4.7 | 142.9 | 0.2 | 201.3 | 202.7 | 1.4 | 10d g | |
|
| |||||||||||
| PBE1PBE | 6-31G*/VTZ | 170.7 | −2.4 | 116.5 | −0.3 | 140.2 | −2.5 | 199.2 | 201.3 | 2.1 | f |
|
| |||||||||||
| M062Xd | Lanl2DZ | 231.1 | 58 | 118.2 | 1.4 | 125.8 | −16.9 | 203.0 | 202.0 | −1.0 | f |
|
| |||||||||||
| M06L | 6-31G*/VTZ | 172.2 | −0.9 | 118.0 | 1.2 | 140.2 | −2.5 | 200.6 | 202.6 | 2.0 | f |
| 6-31+G*(N,O)b/VTZ | 172.4 | −0.7 | 118.1 | 1.3 | 140.7 | −2.0 | 200.8 | 203.1 | 2.3 | f | |
| 6-31G*/TZVP | 172.0 | −1.1 | 117.9 | 1.1 | 141.5 | −1.2 | 201.1 | 203.2 | 2.1 | f | |
| 6-31+G*(N,O)b/TZVP | 172.4 | −0.7 | 118.1 | 1.3 | 140.9 | −1.8 | 201.1 | 203.3 | 2.2 | f | |
| 6-31G*/Lanl2DZ | 172.2 | −0.9 | 117.8 | 1.0 | 140.2 | −2.5 | 200.2 | 202.7 | 2.5 | f | |
| Lanl2DZc | 173.5 | 0.4 | 121.9 | 5.1 | 141.9 | −0.8 | 200.6 | 202.5 | 1.9 | f | |
|
| |||||||||||
| LC-BP86 | 6-31G*/VTZ | 170.9 | −2.2 | 115.2 | −1.6 | 139.1 | −3.6 | 196.1 | 197.5 | 1.4 | f |
|
| |||||||||||
| ωB97X-D | 6-31G*/VTZ | 172.6 | −0.5 | 116.5 | −0.3 | 139.3 | −3.4 | 199.8 | 201.2 | 1.4 | f |
| 6-31+G*(N,O)b/VTZ | 172.3 | −0.8 | 116.6 | −0.2 | 139.7 | −3.0 | 199.9 | 201.5 | 1.6 | f | |
a
basis sets: 6-31G* for H, C, N and O; VTZ, TZVP or Lanl2DZ for Fe;
b
basis set: 6-31G* for H and C, 6-31+G* for N and O.
c
basis set Lanl2DZ for all the atoms.
d
basis set VTZ, TZVP for Fe is also applied, but failed to obtain the converged wave functions.
e
values for Fe-Nshort and Fe-Nlong (Nshort= the average of two short Fe and porphyrin N-atom, Nlong= the average of two long Fe and porphyrin N-atom; Δlong-short is the difference between the experimental data and calculation with corresponding bond lengths and angle.
f
this work.
g
only isotropic terms, for anisotropic terms, see this work