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Yu.B. Vassiliev V.S. Bagotzky O.A. Khazova N.A. Mayorova 《Journal of Electroanalytical Chemistry》1985,189(2):295-309
The mechanism of electroreduction of carbon dioxide in aprotic solvents on mercury, lead, tin, indium and platinum is studied using the photoemission method and the method of stationary polarization curves. When comparing the data of photoemission and “dark” (polarization) measurements it was found that in the first Tafel region of the polarization curves the rate-determining step is the transfer of the second electron to (CO2).?2 anion-radicals formed as a result of the interaction of initially generated CO.?2 anion-radicals with adsorbed CO2 molecules. In the second Tafel region the rate-determining step is the transfer of the first electron to an adsorbed CO2 molecule. The peculiarities of electroreduction of carbon dioxide in aprotic solvents can be explained provided that the effect of potential on adsorption of CO2 and anion-radicals and the effect of repulsion of negatively charged radicals are taken into account. 相似文献
3.
Yu.B. Vassiliev V.S. Bagotzky O.A. Khazova V.V. Cherny A.M. Meretsky 《Journal of Electroanalytical Chemistry》1979,98(2):273-282
The catalytic liquid-phase hydrogenation of maleic acid on platinum and rhodium has been investigated. It is shown that the rate-determining step of this process as well as of the electroreduction process of maleic acid is the interaction of the chemisorbed particle of maleic acid with the adsorbed hydrogen which is formed at the preceding rapid stage of either the dissociative adsorption of molecular hydrogen, or the electrochemical stage of hydrogen ion discharge. The rate of the process with the same degree of surface coverage with hydrogen and chemisorbed particles of maleic acid does not depend on whether the process is carried out catalytically or electrochemically, on whether maleic acid and hydrogen were preliminarily adsorbed on the surface of the electrode-catalyst or not. With due regard for the mutual influence of chemisorbed particles participating in the rate-determining stage, the main kinetic equations for the electroreduction and catalytic hydrogenation processes have been derived. The difference in the rates of electroreduction of maleic acid on platinum and rhodium, with the same degree of electrode surface coverage with reactants, is shown to be the result of differences in the adsorption heats (or bonding strength with the surface) of hydrogen and maleic acid on these two metals. Experimental procedures are described in Part I [1]. 相似文献
4.
V.E. Kazarinov Yu.B. Vassiliev V.N. Andreev S.A. Kuliev 《Journal of Electroanalytical Chemistry》1981,123(2):345-350
The influence of the adsorption potential on the composition of formaldehyde chemisorption products on platinum has been investigated by the radioactive tracer method in conjunction with electrochemical methods. It is shown that in the potential range 0.0–0.3 V the main adsorption product of formaldehyde is a particle of composition COH, and at the potential 0.4 V a particle of composition CO. It has been found that at E<0.3 V adsorbed CO particles are reduced to COH particles. The electrochemical properties of these particles have been studied. 相似文献
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Dmitri Vassiliev 《General Relativity and Gravitation》2002,34(8):1239-1265
In abstract Yang–Mills theory the standard instanton construction relies on the Hodge star having real eigenvalues which makes it inapplicable in the Lorentzian case. We show that for the affine connection an instanton-type construction can be carried out in the Lorentzian setting. The Lorentzian analogue of an instanton is a spacetime whose connection is metric compatible and Riemann curvature irreducible (pseudoinstanton). We suggest a metric-affine action which is a natural generalization of the Yang–Mills action and for which pseudoinstantons are stationary points. We show that a spacetime with a Ricci flat Levi-Civita connection is a pseudoinstanton, so the vacuum Einstein equation is a special case of our theory. We also find another pseudoinstanton which is a wave of torsion in Minkowski space. Analysis of the latter solution indicates the possibility of using it as a model for the neutrino. 相似文献
7.
Renat R. Nazmutdinov Tamara T. Zinkicheva Sergey Yu. Vassiliev Dmitri V. Glukhov Galina A. Tsirlina Michael Probst 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(4):1244-1252
The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms (“dimers”) was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition. 相似文献
8.
We study the theory of the structure induced by parameter free formulas on a “dense” algebraically independent subset of a model of a geometric theory T. We show that while being a trivial geometric theory, inherits most of the model theoretic complexity of T related to stability, simplicity, rosiness, the NIP and the NTP2. In particular, we show that T is strongly minimal, supersimple of SU‐rank 1, has the NIP or the NTP2 exactly when has these properties. We show that if T is superrosy of thorn rank 1, then so is , and that the converse holds if T satisfies acl = dcl. 相似文献
9.
In this paper we develop a new approach to the theory of Fourier integral operators. It allows us to represent the Schwartz kernel of a Fourier integral operator by one oscillatory integral with a complex phase function. We consider Fourier integral operators associated with canonical transformations, having in mind applications to hyperbolic equations. As a by-product we obtain yet another formula for the Maslov index. © 1994 John Wiley & Sons, Inc. 相似文献
10.
We have studied the possibility to detect vector mesons via their decay into μ+μ− pairs in heavy-ion collisions at FAIR with a muon detection system as part of the Compressed Baryonic Matter (CBM) experiment.
The text was submitted by the authors in English. 相似文献