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This collision diameter assumes no ligand interdigitation in the activated complex. Interdigitation would slightly elevate the estimated outersphere reorganizational energy
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This collision diameter assumes no ligand interdigitation in the activated complex. Interdigitation would slightly elevate the estimated outersphere reorganizational energy.
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The chosen dielectric constants assume that the εop and εs environment of the MPC core is determined by the-SC2Ph ligands, that is, assume that effects of CH2C2 solvent intrusion are negligible. εop values of the two phases differ little, but εs values differ more. Assuming an εs core environment of solely CH2Cl2 would increase ΔGOS (but still fall far short of the large observed Ea) and decrease the ΔGis to around 30, The true value for Au25 is probably somewhere in between. That solvent intrusion into MPC monolayers on Au140 MPCs is not a dominant factor in electron transfer (outer sphere) dynamics was suggested by results 42 for Au140 MPCs where neglecting intrusion effects gave AGOS estimates most consistent with experimental results
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OS estimates most consistent with experimental results.
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