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Alexander M Kuznetsov

Publications and source records attributed to Alexander M Kuznetsov.

7 recordsLinked to original sources
PubMed2006

Mechanism of electrochemical charge transport in individual transition metal complexes.

We used electrochemical scanning tunneling microscopy (STM) and spectroscopy (STS) to elucidate the mechanism of electron transport through individual pyridyl-based Os complexes. Our tunneling data obtained by two-dimensional electrochemical STS and STM imaging lead us to the conclusion that electron transport occurs by thermally activated hopping. The conductance enhancement around the redox potential of the complex, which is reminiscent of switching and transistor characterics in electronics, is reflected both in the STM imaging contrast and directly in the tunneling current. The latter shows a biphasic distance dependence, in line with a two-step electron hopping process. Under conditions where the substrate/molecule electron transfer (ET) step is dominant in determining the overall tunneling current, we determined the conductance of an individual Os complex to be 9 nS (Vbias = 0.1 V). We use theoretical approaches to connect the single-molecule conductance with electrochemical kinetics data obtained from monolayer experiments. While the latter leave some controversy regarding the degree of electronic coupling, our results suggest that electron transport occurs in the adiabatic limit of strong electronic coupling. Remarkably, and in contrast to established ET theory, the redox-mediated tunneling current remains strongly distance dependent due to the electronic coupling, even in the adiabatic limit. We exploit this feature and apply it to electrochemical single-molecule conductance data. In this way, we attempt to paint a unified picture of electrochemical charge transport at the single-molecule and monolayer levels.

Journal Article↗
PubMed2006

Effect of low-level alpha-radiation on bioluminescent assay systems of various complexity.

This study addresses the effects of low-level alpha-radiation on bioluminescent assay systems of different levels of organization: in vivo and in vitro. Three bioluminescent assay systems are used: intact bacteria, lyophilized bacteria, and bioluminescent system of coupled enzyme reactions. Solutions of 241Am(NO3)3 are used as a source of alpha-radiation. It has been shown that activation processes predominate in all the three bioluminescent assay systems subjected to short-term exposure (20-55 h) and inhibition processes in the systems subjected to longer-term exposure to radiation. It has been found that these effects are caused by the radiation component of 241Am3+ impact. The intensity of the 241Am3+ effect on the bioluminescent assay systems has been shown to depend on the 241Am3+ concentration, level of organization and integrity of the bioluminescent assay system. The bioluminescent assay systems in vivo have been found to be highly sensitive to 241Am3+ (up to 10(-17) M).

Alpha Particles↗
PubMed2006

In situ superexchange electron transfer through a single molecule: a rectifying effect.

An increasingly comprehensive body of literature is being devoted to single-molecule bridge-mediated electronic nanojunctions, prompted by their prospective applications in molecular electronics and single-molecule analysis. These junctions may operate in gas phase or electrolyte solution (in situ). For biomolecules, the latter is much closer to their native environment. Convenient target molecules are aromatic molecules, peptides, oligonucleotides, transition metal complexes, and, broadly, molecules with repetitive units, for which the conducting orbitals are energetically well below electronic levels of the solvent. A key feature for these junctions is rectification in the current-voltage relation. A common view is that asymmetric molecules or asymmetric links to the electrodes are needed to acquire rectification. However, as we show here, this requirement could be different in situ, where a structurally symmetric system can provide rectification because of the Debye screening of the electric field in the nanogap if the screening length is smaller than the bridge length. The Galvani potentials of each electrode can be varied independently and lead to a transistor effect. We explore this behavior for the superexchange mechanism of electron transport, appropriate for a wide class of molecules. We also include the effect of conformational fluctuations on the lowest unoccupied molecular orbital (LUMO) energy levels; that gives rise to non-Arrhenius temperature dependence of the conductance, affected by the molecule length. Our study offers an analytical formula for the current-voltage characteristics that demonstrates all these features. A detailed physical interpretation of the results is given with a discussion of reported experimental data.

Electric Conductivity↗
PubMed2006

Effect of internal conversion of vibrational quanta in electron tunneling: a scheme for direct experimental observation and current/voltage relationships.

Electron tunneling through bridge molecular groups with a strong coupling to a local quantum vibrational mode is considered. A scheme is suggested for direct experimental observation of the effect of internal conversion of vibrational quanta in inelastic electron tunneling. The effect consists of excitation and re-absorption of vibrational quanta in bridge by tunneling electrons. The tunnel current produced by the absorption of vibrational quanta by the same or another electron can in principle be detected in an experimental setup a scheme of which is suggested. Current/voltage dependences have general spectroscopic features. Possible effects that can take place in the case of additional strong interaction with classical vibrational modes are discussed.

Journal Article↗
PubMed2005

Quantum mechanical model for the dissociative adsorption of diatomic molecules on metal surfaces.

A quantum mechanical nonadiabatic theory of dissociative adsorption of diatomic molecules X2 on metal surface is presented. The following reaction coordinates are used to construct crossing diabatic potential energy surfaces (PES): the distance y between the atoms of the X2 molecule, the distance x of the X2 molecular axis from the surface, the set of coordinates describing possible displacements of metal atoms under adsorption. Expression for the rate constant is derived using the model potentials describing vibrations along these coordinates. The calculated dependency of the rate constant W on the reaction heat DeltaE is compared with that in classical approximation. It is shown that quantum effects lead to a weaker dependence of W on DeltaE as compared to that for classical one.

Journal Article↗
PubMed2004

Electron correlation effects in the adiabatic charge transfer reactions at the metal/polar liquid interface.

New simple expressions for average number of electrons in the valence orbital of a reacting ion and the charge susceptibility are obtained that allow one to calculate adiabatic free energy surfaces (AFES) and corresponding kinetic regime diagrams (KRD) for adiabatic processes of electron transfer from the ion, located in a polar liquid, to a metal within the framework of the exactly solvable (in the limit T-->0) model of the metal with the infinitely wide conduction band. This model represents one of limiting cases of the Anderson model that may be applied to s-p metals. Unlike previous studies of the adiabatic reactions in the model of the metal with the infinitely wide conduction band, the present work takes into account the electron-electron correlation effects in an exact manner. General results are illustrated with KRD which determine the regions of the physical parameters of the system corresponding to various types of electron transfer processes. AFES are calculated for some typical parameters sets. The exact AFES are compared with those calculated within the Hartree-Fock approximation. It is shown that the correlation effects are of importance and results not only in a considerable decrease of the activation free energy but also to qualitatively different shapes of AFES in some regions of the system parameters.

Journal Article↗