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E G Petrov

Publications and source records attributed to E G Petrov.

16 recordsLinked to original sources
PubMed2004

Bridge mediated two-electron transfer reactions: on the influence of intersite Coulomb interactions.

Donor-acceptor two-electron transfer (TET) mediated by a linear molecular bridge is described theoretically. The particular case is considered where the TET takes place in the presence of a strong electronic intersite coupling within the bridge and against the background of fast vibrational relaxation processes. For such a situation the coarse-grained description of bridge-assisted electron transfer in molecular systems can be utilized [Petrov et al., J. Phys. Chem. B 106, 3092 (2002)]. In the present case it leads to kinetic equations and rate expression for TET reactions. Our recent treatment of completely nonadiabtic TET reactions [Petrov et al., J. Chem. Phys. 120, 4441 (2004)] including a reduction to single-exponential kinetics (with overall transfer rate K(TET)) is generalized here to the case of strong intrabridge coupling and the presence of intersite Coulomb interactions. The dependence of K(TET) on the bridge length which is determined by a separate stepwise and concerted contribution is discussed in detail. It is found that the intersite Coulomb interaction favors the TET if the donor and the acceptor are uncharged in their completely reduced states (with two excess electrons present).

Journal Article↗
PubMed2004

Bridge mediated two-electron transfer reactions: analysis of stepwise and concerted pathways.

A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D-(-)BA with the product state DBA-(-) results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate KTET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D-B-A, DB-(-)A, D-BA-, and DB-A-, KTET is obtained as a sum of the rates KTET(step) and KTET(sup). The first rate describes stepwise TET originated by transitions of a single electron. It starts at D-(-)BA and reaches DBA-(-) via the intermediate state D-BA-. These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D-(-)BA to DBA-(-) defines KTET(sup). An analytic dependence of KTET(step) and KTET(sup) on the number of bridging units is presented and different regimes of D-A TET are studied.

Journal Article↗
PubMed2003

Two-electron transfer reactions in proteins: bridge-mediated and proton-assisted processes.

Nonadiabatic two-electron transfer (TET) reactions through donor-bridge-acceptor (DBA) systems is investigated within the approximation of fast vibrational relaxation. For TET reactions in which the population of bridging states remains small (less than 10(-2)) it is demonstrated that a multiexponential transition process reduces to three-state kinetics. The transfer starts at the state with two excess electrons at the D center (D(2-)BA), goes through the intermediate (transient) state with one electron at the D center and one at the A center (D-BA-), and ends up with the two electrons at the A center (DBA2-). Furthermore, if the population of the intermediate state becomes also small the two-exponential kinetics can be transformed with high accuracy to single-exponential D-A TET kinetics. The related overall transfer rate contains contributions from stepwise and from concerted TET. The latter process is determined by a specific two-electron superexchange coupling incorporating the bridging states (D-B-A and DB-A-) as well as the intermediate state (D-BA-). As an example, the reduction of micothione reductase by nicotinamide adenine dinucleotide phosphate is analyzed. Existing experimental data can be explained if one assumes that the proton-assisted reduction of the enzyme is realized by the concerted TET mechanism.

Electron Transport↗
PubMed2001

Nonlinear electron current through a short molecular wire.

The voltage and the temperature behavior of inelastic interelectrode current mediated by a short molecular wire is analyzed within a nonlinear kinetic approach that accounts for strong Coulomb repulsion between transferring electrons. When the coupling to the heat bath occurs via high-frequency vibration modes we predict a generally nonlinear current-voltage characteristics (an Ohmic behavior at small voltage, rising towards saturation and being followed by an abrupt decrease at large voltage) and a bell-shaped current response vs temperature at not too large temperatures.

Journal Article↗
PubMed1999

Influence of a periodic field on the distant electron transfer in biological systems.

Generalization of the Marcus transfer rate is derived for the case of a dissipative long-range donor-acceptor electron transfer (ET) mediated by specific bridging electron pathways in biological systems and driven by ac-electric field. High-frequency electric field is shown to block and even to invert the transfer if a specific relation between amplitude and frequency of the ac-field is fulfilled.

Electricity↗
PubMedDate not supplied

[Kinetic model of the effect of dehydration on electron transfer from membrane-bound cytochrome c to the photosynthetic reaction center].

Amplitude characteristics and kinetics of laser-induced oxidation of high-potential cytochrome CH by a photosynthetic reaction center (RC) were investigated in Ectothiorhodospira shaposhnikovii chromatophore preparations of various humidity. It is shown that the diminuition of the amount of oxidized cytochrome and the decrease of the rate of the reaction on lowering the preparation humidity can be explained in terms of the concept of conformation-controlled electron transfer within the CH-RC complex. A model is suggested which predicts that the reversible transition of the complex from one conformational state which allows electron transfer ("contact" state) to the other in which the transfer is impossible ("non-contact" state) is the result of drying (or low temperature) induced changes in the electron tunnelling path in the region of "contact" of the cytochrome CH and RC protein globules.

Bacteria↗
PubMedDate not supplied

[Electron-conformation transitions in the complex of bacterial photosynthetic reaction centers with cytochromes].

A theoretical model of conformation--regulated electron transfer from multihaem cytochrome c to bacteriochlorophyll of the reaction centre (RC) is considered. The theoretical data are compared with the experimental ones on the basis of temperature dependence of laser-induced electron transfer from high-potential cytochrome Ch bacheriochlorophyll of RC in Ectothiohodospira shaposhnikovii chromatophores. From this comparison there were calculated the thermodynamic characteristics of cytochrome Ch transfer from the configuration without electron transfer to RC bacteriochlorophyll into the coordinated configuration with an effective transfer. The values obtained are: H = 7,1 kJ/M; S = --(30,2--36,9) J/grad. M. Possible regulatory role of such conformation transitions is discussed.

Bacterial Proteins↗
PubMedDate not supplied

[Charge separation in bacterial photosynthetic reaction centers].

The physical aspects of the primary charge separation process in bacterial photosynthesis are discussed. The donor-acceptor model of electron tranfer through proteins is used. The kinetics of the processes of the photosynthetic reaction centers are considered and their energetic scheme is constructed by means of the nonequilibrium density matrix method. It is shown that the theory is in good agreement with experiment if one takes into account the influence of vibrational sublevels of states which take part in transitions.

Bacteria↗