An infinite bandwidth limit model for adiabatic electrochemical electron transfer including electron correlation effects: the exact solution

On the possibility of an STM-induced dissociative electron transfer

“…If parameters of the system lie in a critical region, then AFES displays two potential wells and, consequently, there is a possibility of the occurrence of processes of electron transfer. Making use of formulas (24) and (25) given in [14], we find that the equation for critical curves has the form D)]. At γ = 1, or at ∆ = 2(1 + D)/π) (eη) * = 0.…”

“…As was the case with common adiabatic processes of electron transfer [24][25][26], for adiabatic processes of…”

“…which is a trivial matter to demonstrate using formulas (24) and (25). The set of formulas (23), (26), and (27) for q s in the general case has either one solution or three solutions.…”

Effect of electron-electron correlations on the activation free energy of adiabatic electrochemical reactions of dissociative electron transfer

“…The solution in question was further modified in works [15,18] for a description of adiabatic electrochemical reactions of electron transfer. Of essence is that this solution exactly took into account effects of electron-electron correlations.…”

“…However, this approach ignored effects of electron-electron correlations following the filling of the antibonding orbital of a molecule. At the same time, the latter may play a substantial role in the kinetics of an elementary act of an electron transfer process and lead not only to quantitative corrections to kinetic parameters but also to qualitative differences in the paths of reactions [11][12][13][14][15][16][17][18]. To investigate effects of electron-electron correlations in adiabatic electrochemical reactions of dissociation with use made of an exact solution of the Anderson model, which was obtained for an electrode with an infinitely broad conduction band is precisely the goal of this work.…”