Gate-tunable electroluminescence in Aviram-Ratner-type molecules: Kinetic description.

A theoretical study of the mechanisms of electroluminescence (EL) generation in photoactive molecules with donor and acceptor centers linked by saturated σ-bonds (molecules of the Aviram-Ratner-type) is presented. The approach is based on the kinetics of single-electron transitions between many-body molecular states. This study shows that the EL polarity arises due to asymmetric coupling of molecular orbitals of the photochromic part of the molecule to the electrodes. The gate voltage controls the power of the EL through the occupancy of the excited singlet state. The shifting of the orbital energies forms a resonant or a non-resonant path for the transmission of electrons through the molecule. The action of the gate voltage is reflected in specific critical voltages. An analytical dependence of the critical voltages on the energies of molecular states involved in the formation of EL, as well as on the gate voltage, was derived for both positive and negative polarities. Conditions under which the gate voltage lowers the absolute value of the bias voltage that is responsible for the activation of the resonance mechanism of EL formation were also established. This is an important factor in control of EL in molecular junctions.

Theory of Triplet Excitation Transfer in the Donor-Oxygen-Acceptor System: Application to Cytochrome b6f.

Theoretical consideration is presented of the triplet excitation dynamics in donor-acceptor systems in conditions where the transfer is mediated by an oxygen molecule. It is demonstrated that oxygen may be involved in both real and virtual intramolecular triplet-singlet conversions in the course of the process under consideration. Expressions describing a superexchange donor-acceptor coupling owing to a participation of the bridging twofold degenerate oxygen's virtual singlet state are derived and the transfer kinetics including the sequential (hopping) and coherent (distant) routes are analyzed. Applicability of this theoretical description to the pigment-protein complex cytochrome b6f, by considering the triplet excitation transfer from the chlorophyll a molecule to distant ß-carotene, is discussed.