Exact(5)
Laser control of ultrafast double proton transfer is investigated for a two-dimensional model system describing stepwise and concerted transfer pathways.
Special emphasis is paid to the relative importance of stepwise and concerted transfer pathways for the driven wave packet and its dependence on the parameters of the model Hamiltonian as well as on the propagation time.
While stepwise transfer is dominating in all cases considered, for high barrier systems concerted transfer proceeding via tunneling can make a contribution.
In my view, the best hope lies in what is already happening: a concerted transfer of presidential power from Mubarak to a trio consisting of his Vice President Omar Suleiman, the Defense Minister Mohammed Tantawi, and retired General Ahmed Shafiq, the newly appointed Prime Minister.
Also, donation of a proton from FeIII-OH– would result in the formation of a terminal iron oxide species or would require the concerted transfer of a second proton from another site, which is not supported by the proton inventory.
Similar(54)
These four points guide the successful application of the extended Marcus theory, which has broad relevance to interpretation of charge transfer data, including multiple-site concerted electron proton transfer reaction data.
With these considerations, one can understand why (electronically) adiabatic ET implies electronically adiabatic PT (overall, an electronically adiabatic double-charge transfer reaction) for both the stepwise and concerted electron proton transfer reactions.
The first is the mechanistic requirement for catalyzing oxidative decarboxylation via a concerted decarboxylation/proton transfer transition state.
These reactions generally involve a substantially concerted atom transfer from the oxidant to an organic substrate, driven by the release of ring strain and by the formation of a strong carbonyl, imine, or oxometal π-bond.
The proper tuning of the reduction potentials is fundamental to achieve concerted e−/H+ transfer, which contributes to cellular energy transduction, which is intimately linked to the nature of the residue at position 58.
Thermal averaging was also performed by Kuznetsov and Ulstrup, with the main focus on PT, concerted electron proton transfer, and applications to HAT in enzymatic reactions studied by Klinman and co-workers.
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