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See Supporting Information for details.
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Clearly, van der Waals interactions will play a role in favoring the formation of the precoordination complex. However, DFT methods are well-known to completely neglect these attractive forces. Thus, our energy estimates must be taken as upper limits with the real values probably being 2-3 kcal/mol lower than computed.
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57
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Note that we indicate transition states in Figures 1 and 3 that connect the free reactants with the precoordination complexes. These transition states cannot be located reliably using standard transition searches that samply the electronic energy surface, because they are highly dominated by translational entropy changes. A more detailed discussion of this problem can be found, e.g., in ref 65
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The electronic structure of 2-TS1 was calculated with the restricted spin formalism. As pointed out by a reviewer, it is possible that our computed configuration is only stable as a result of the restricted formalism. Thus, we have repeated the calculations in the unrestricted spin framework and found our proposed wave function to be stable.
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4644276530
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See Computational Details for an overview of the different terms.
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68
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4644248501
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note
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The use of B3LYP/6-31G** in geometry optimization also gave activation energies that were ∼4 kcal/mol too low (see Supporting Information). Thus, we contribute ∼5 kcal/mol of the disagreement to the smaller basis set and ∼5 kcal/mol to the use of BLYP instead of B3LYP. Note that the hybrid functional B3LYP requires Hartree-Fock calculations, which are not available in pure DFT packages, such as ADF.
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69
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We use the energy unit eV in addition to kcal/mol to avoid nonintuitively large numerical values that would be required for for the Ziegler-Rauk terms.
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