Biochemistry and theory of proton-coupled electron transfer.
Affiliation: Department of Chemistry, ‡Department of Biochemistry, and §Department of Physics, Duke University , Durham, North Carolina 27708, United States.Show MeSH
Mentions: Equation 5.43 is the Schrödinger equationfor the (reactive) electron atfixed nuclear coordinates within the BO scheme. Therefore, ϕαad is theelectronic component of a BO product wave function that approximatesan eigenfunction of the total Hamiltonian at x valuesfor which the BO adiabatic approximation is valid. In fact, theseadiabatic states give Vαβ = Eαδαβ, butcorrespond to (approximate) diagonalization of the full Hamiltonian (eq 5.1) only forsmall nonadiabatic kinetic coupling terms. We now (i) analyze andquantify, for the simple model in Figure 24, features of the nonadiabatic coupling between electronic statesinduced by the nuclear motion that are important for understandingPCET (therefore, the nonadiabatic coupling terms neglected in theBO approximation will be evaluated in the analysis) and (ii) showhow mixed electron–proton states of interest in coupled ET–PTreactions are derived from the analysis of point i.
Affiliation: Department of Chemistry, ‡Department of Biochemistry, and §Department of Physics, Duke University , Durham, North Carolina 27708, United States.