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Note that this is a computational simplification. Since no optimizations were performed at the TZVPP level, frequency calculations would be meaningless. While the difference in methods does introduce some error, this error is small in comparison to the total energy. The important point is that the relative free energy corrections must be consistent, which is the case
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Note that this is a computational simplification. Since no optimizations were performed at the TZVPP level, frequency calculations would be meaningless. While the difference in methods does introduce some error, this error is small in comparison to the total energy. The important point is that the relative free energy corrections must be consistent, which is the case.
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This method uses a linear synchronous transit or quadratic synchronous transit approach to get closer to the quadratic region around the transition state and then uses a quasi-Newton or eigenvector-following algorithm to complete the optimization. It is started with the keywords QST2 and QST3, where QST2 requires two molecule specifications (for the reactant and product) as its input, while QST3 requires three molecule specifications for the reactant, the product, and an initial structure of the transition state
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This method uses a linear synchronous transit or quadratic synchronous transit approach to get closer to the quadratic region around the transition state and then uses a quasi-Newton or eigenvector-following algorithm to complete the optimization. It is started with the keywords QST2 and QST3, where QST2 requires two molecule specifications (for the reactant and product) as its input, while QST3 requires three molecule specifications (for the reactant, the product, and an initial structure of the transition state).
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Zero-point corrections cannot be computed if a rigid PES scan is performed, since the structures are not fully optimized at each step of the scan and frequency calculations are meaningless unless the structure is fully optimized. Full optimizations at each point were considered unnecessary, since the exact energy has already been calculated and the point was simply to ascertain whether our results were consistent with this previously calculated value
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While the assignment of double-bond character to Fe=0 is somewhat arbitrary, the bond length of 1.714 Å is much closer to the bond length of 1.614 Å in the FeIV=O product than to that of 1.916 Å in the FeII reactant. More significantly, it is slightly shorter than the Fe-O bond length in [L2FeIII(OH)(NCCH 3)]2+ and 0.1 Å shorter than the terminal Fe-O distance in the only characterized FeIII=O complex
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III=O complex.
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