1,720,992 research outputs found
Irreversibility in redox molecular conduction: single versus double metal-molecule interfaces
No full textIn this work we analyze the onset and manifestation of irreversibility phenomena in the charge transport at single and double metal-redox molecule interfaces, with special emphasis on the role of the nuclear system reorganization energy in causing the distortion of cyclic voltammograms in the first case and the occurrence of hysteresis phenomena in the second case. Under physical conditions for which two states of the molecular system come into play, effects of irreversibility increase with the reorganization energy at a single interface, while an opposite trend is seen in the conduction through a molecular junction. The apparent contradiction between these two behaviors, which was raised in a previous work (Migliore, A.; Nitzan, A.; J. Am. Chem. Soc. 2013, 135, 9420-32) is here resolved through detailed investigation of the connections between molecule reorganization energy, bias-dependent population of the molecular redox site(s), and threshold voltage scan rate for the onset of irreversible behavior. Moreover, our investigation of the effects of the reorganization energy on the voltammogram peaks proposes a strategy for extracting the value of the reorganization energy of the molecular system from the experimental behavior
Nonlinear Charge Transport in Redox Molecular Junctions: A Marcus Perspective
No full textRedox molecular junctions are molecular conduction junctions that involve more than one oxidation state of the molecular bridge. This property is derived from the ability of the molecule to transiently localize transmitting electrons, implying relatively weak molecule-leads coupling and, in many cases, the validity of the Marcus theory of electron transfer. Here we study the implications of this property on the nonlinear transport properties of such junctions. We obtain an analytical solution of the integral equations that describe molecular conduction in the Marcus kinetic regime and use it in different physical limits to predict some important features of nonlinear transport in metal-molecule-metal junctions. In particular, conduction, rectification, and negative differential resistance can be obtained in different regimes of interplay between two different conduction channels associated with different localization properties of the excess molecular charge, without specific assumptions about the electronic structure of the molecular bridge. The predicted behaviors show temperature dependences typically observed in the experiment. The validity of the proposed model and ways to test its predictions and implement the implied control strategies are discussed. © 2011 American Chemical Society
Irreversibility and Hysteresis in Redox Molecular Conduction Junctions
No full textIn this work we present and discuss theoretical models of redox molecular junctions that account for recent observations of nonlinear charge transport phenomena, such as hysteresis and hysteretic negative differential resistance (NDR). A defining feature in such models is the involvement of at least two conduction channels - a slow channel that determines transitions between charge states of the bridge and a fast channel that dominates its conduction. Using Marcus' theory of heterogeneous electron transfer (ET) at metal-molecule interfaces we identify and describe different regimes of nonlinear conduction through redox molecular bridges, where the transferring charge can be highly localized around the redox moiety. This localization and its stabilization by polarization of the surrounding medium and/or conformational changes can lead to decoupling of the current response dynamics from the time scale of the voltage sweep (that is, the current does not adiabatically follow the voltage), hence to the appearance of memory (thermodynamic irreversibility) in this response that is manifested by hysteresis in current-voltage cycles. In standard voltammetry such irreversibility leads to a relative shift of the current peaks along the forward and backward voltage sweeps. The common origin of these behaviors is pointed out, and expressions of the threshold voltage sweep rates are provided. In addition, the theory is extended (a) to analyze the different ways by which such phenomena are manifested in single sweep cycles and in ensemble averages of such cycles and (b) to examine quantum effects in the fast transport channel. © 2013 American Chemical Society
On the evaluation of the Marcus-Hush-Chidsey integral
No full textThe electrochemical rate constant obtained from the Marcus-Hush theory of heterogeneous electron transfer is given as a relatively complex integral. Recently, two apparently different expressions of this rate constant in the form of a series of analytical functions appeared in the literature. We demonstrate here the equivalence of these expressions and discuss their different approximations, resulting from the two distinct analytical derivations, which have implications in the practical calculation of electron transfer rate constants at electrode surfaces. © 2012 Elsevier B.V. All rights reserved
On the relationship between molecular state and single electron pictures in simple electrochemical junctions
No full textWe consider a molecular conduction junction that comprises a redox molecule bridging between metal electrodes, in the limit of weak coupling and high temperature where electron transport is dominated by Marcus electron transfer kinetics. We address the correspondence between the Marcus description in terms of nuclear potential energy surfaces associated with different charging states of the molecular bridge, and the single electron description commonly used in theories of molecular conduction. The relationship between the energy gap, reorganization energy and activation energy parameters of the Marcus theory and the corresponding energy parameters in the single electron description is elucidated. We point out that while transport in the normal Marcus regime involves activated (therefore relatively slow) transitions between at least two charging states of the molecular bridge, deep in the inverted regime only one of these states is locally stable and transitions into this state are activationless. The relatively slow rates that characterize the normal Marcus transport regime manifest themselves in the appearance of hysteresis in the system transport behavior as a function of gate or bias potentials for relatively slow scan rates of these potentials, but not bistability in the junction conduction behavior. We also consider the limit of fast solvent reorganization that may reflect the response of the electronic environment (electronic polarization of a solvent and of the metal electrodes) to the changing charging state of the bridge. In this limit, environmental reorganization appears as renormalization of the bridge electronic energy levels. We show that the effect of this reorganization on the junction conduction properties is not universal and depends on the particular bridge charging states that are involved in the conduction process. This journal is © 2012 the Owner Societies
Quantum transport with two interacting conduction channels
No full textThe transport properties of a conduction junction model characterized by two mutually coupled channels that strongly differ in their couplings to the leads are investigated. Models of this type describe molecular redox junctions (where a level that is weakly coupled to the leads controls the molecular charge, while a strongly coupled one dominates the molecular conduction), and electron counting devices in which the current in a point contact is sensitive to the charging state of a nearby quantum dot. Here we consider the case where transport in the strongly coupled channel has to be described quantum mechanically (covering the full range between sequential tunneling and co-tunneling), while conduction through the weakly coupled channel is a sequential process that could by itself be described by a simple master equation. We compare the result of a full quantum calculation based on the pseudoparticle non-equilibrium Green function method to that obtained from an approximate mixed quantum-classical calculation, where correlations between the channels are taken into account through either the averaged rates or the averaged energy. We find, for the steady state current, that the approximation based on the averaged rates works well in most of the voltage regime, with marked deviations from the full quantum results only at the threshold for charging the weekly coupled level. These deviations are important for accurate description of the negative differential conduction behavior that often characterizes redox molecular junctions in the neighborhood of this threshold. © 2013 AIP Publishing LLC
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Full text linkWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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