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L. D. Zusman 《Theoretical and Experimental Chemistry》1985,21(1):25-31
A general solution of the problem of finding the rate constant of electron-transfer reactions in polar solvents without the restrictions of the diffusional approximation has been obtained. Expressions for the reaction rate constant at the limit of the random-jump mechanism, as well as a convenient equation describing the transition between the random-jump and diffusional reaction mechanisms, have been found. A test for identifying a random-jump electron-transfer mechanism has been proposed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 27–33, January–February, 1985. 相似文献
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Homogeneous and electrochemical two-electron transfers within the Tl(aq)(3+)/Tl(aq)(+) couple are considered on a common conceptual basis. For the 2 equiv electrochemical reduction of Tl(aq)(3+) to Tl(aq)(+), the intermediate state with a formal reduction potential, E(1) = 1.04 +/- 0.10 V vs the normal hydrogen electrode, was detected, different from the established value of 0.33 V for a Tl(3+)/Tl(2+) couple. Examination of obtained electrochemical (cyclic voltammetry (CV) and rotating disk electrode techniques, along with the CV-curve computer simulation procedure) and literature data indicate that the detected formal potential cannot be the property of electrode-adsorbed species, but rather of the covalently interacting dithallium intermediate [Tl(II)-Tl(II)](4+) located at the outer Helmholtz plane. The analysis of microscopic mechanisms, based on the recent hypothesis of H. Taube and the Marcus-Hush theory extended by Zusman and Beratan, and Koper and Schmickler, revealed that the homogeneous process most probably takes place through the superexchange inner-sphere two-electron-transfer mechanism, via an essentially virtual (undetectable) dithallium intermediate. In contrast, the electrochemical process occurs through a sequential mechanism, via the rate-determining step of Tl(aq)(2+) ion formation immediately followed by activationless formation of the metastable (CV-active) dithallium state. The second electrochemical electron-transfer step is fast, and shows up only in the peak height (but not in the shape) of the observed CV cathodic wave. The anodic wave for a microscopically reverse process of the oxidation of Tl(aq)(+) to Tl(aq)(3+) cannot be observed within the considered potential range due to the blocking of through-space electron transfer by the competitor process of ion transfer to the electrode. 相似文献
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We investigate nonlinear oscillations in a fourth-order partialdifferential equation which models a suspension bridge. Previouswork establishes multiple periodic solutions when a parameterexceeds a certain eigenvalue. In this paper, we use Leray-Schauderdegree theory to prove that if the parameter is increased further,beyond a second eigenvalue, then additional solutions are created. 相似文献
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L.D. Zusman 《Chemical physics》1980,49(2):295-304
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L.D. Zusman 《Chemical physics letters》1983,99(4):287-290
It is shown that in the vicinity of the critical point of a binary polar mixture the electronic spectral linewidth increases when approaching the critical point. The linewidth obeys the law of Ao[(T-Tc)/Tc]?γ, where γ is the universal critical index of dispersion of concentration fluctuations. 相似文献
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Poolman HR Boersma DJ Harvey M Higinbotham DW Passchier I Six E Alarcon R van Amersfoort PW Bauer TS Boer Rookhuizen H van Den Brand JF van Buuren LD Bulten HJ Ent R Ferro-Luzzi M Geurts DG Heimberg P de Jager CW Klimin P Koop I Kroes F van Der Laan J Luijckx G Lysenko A Militsyn B Nesterenko I 《Physical review letters》2000,84(17):3855-3858
We report on first measurements with polarized electrons stored in a medium-energy ring and with a polarized internal target. Polarized electrons were injected at 442 MeV (653 MeV), and a partial (full) Siberian snake was employed to preserve the polarization. Longitudinal polarization at the interaction point and polarization lifetime of the stored electrons were determined with laser backscattering. Spin observables were measured for electrodisintegration of polarized 3He, with simultaneous detection of scattered electrons, protons, neutrons, deuterons, and 3He nuclei, over a large phase space. 相似文献
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Rubens R Santos Jr Alexandrina Sartori Deison S Lima Patrícia RM Souza Arlete AM Coelho-Castelo Vania LD Bonato Célio L Silva 《Journal of immune based therapies and vaccines》2009,7(1):4-12