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As noted in ref 25, the Np-Fe-Np bend and the Np(4)-Fe wag have the same internal coordinates. We use the bend definition here
-
As noted in ref 25, the Np-Fe-Np bend and the Np(4)-Fe wag have the same internal coordinates. We use the bend definition here.
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The sombrero mode in Table 6 is not the lowest-frequency doming mode possible. The calculation did not include heme torsional coordinates that would give rise to the low-frequency out-of-plane modes of the macrocycle itself. The present model is consistent with anharmonic coupling involving still lower-frequency modes. This issue was not examined for lack of experimental data to support detailed modeling
-
The sombrero mode in Table 6 is not the lowest-frequency doming mode possible. The calculation did not include heme torsional coordinates that would give rise to the low-frequency out-of-plane modes of the macrocycle itself. The present model is consistent with anharmonic coupling involving still lower-frequency modes. This issue was not examined for lack of experimental data to support detailed modeling.
-
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46
-
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33645907151
-
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note
-
The complexity of the 38-body model may seem unwarranted at first, given that there are 46 stretching force constants, 79 bending force constants, and a large number of torsional and wagging force constants that could be included. However, in the model calculation, the in-plane force constants are fixed, and all torsions, wags, and interaction force constants are ignored. The stretching and bending force constants for the imidazole ring in this calculation have been based on estimates from the pyrrole ring force constants for the in-plane force field (see Supporting Information). The goal of the calculations is to consider the essential degrees of freedom that contribute to an axial out-of-plane mode.
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51
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33645934468
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-
note
-
We have investigated three-body models that include ligand bending within a harmonic approximation. Ligand bending is also included in the six-body and 38-body models. The result of these investigations is that there is no range of bending force constants that can explain the anomalous isotope effects in Figures 4 and 5 with a harmonic approximation.
-
-
-
-
52
-
-
33645917931
-
-
Manuscript in preparation
-
Franzen, S.; Fritsch, K.; Dyer, R. B.; Boxer, S. G.; Frauenfelder, H. Manuscript in preparation.
-
-
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Franzen, S.1
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53
-
-
33645909828
-
-
note
-
-1 with respect to that of H93G(4-Me Im) (data not shown).
-
-
-
-
55
-
-
33645911434
-
-
note
-
a. In the case of the H93G(4-Me Pyr), adduct preparation requires reconstitution of H93G with heme since the ligand cannot be introduced by dialysis. We did not succeed in forming the 2-methyl- or 2-fluoropyridine adducts even with this procedure, suggesting that binding is very weak to deoxyferrous heme iron. It appears that in these cases steric hindrance results in a lowering of the frequency of the Raman mode. This has been suspected to be the origin of the lower frequency of 2-methyl imidazole adducts of iron porphyrins.
-
-
-
-
56
-
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33645929672
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-
Manuscript in preparation
-
Pang, P.; Boxer, S. G. Manuscript in preparation.
-
-
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Pang, P.1
Boxer, S.G.2
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