A semiclassical theory of electron transfer reactions in Condon approximation and beyond

Кузнецов, А. М.; Соколов, В. В.; Ulstrup, Jens

doi:10.1016/s0022-0728(00)00408-3

Cited by 44 publications

(88 citation statements)

References 21 publications

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“…The interaction between vibrations and electronic states is responsible for many of the most important phenomena in molecular materials, including vibrational peaks in electronic spectra, nonadiabatic processes of many types, including JahnTeller distortions, and the characteristic activation processes associated with transport in conducting polymers (60)(61)(62). These same vibronic coupling effects are expected to be extremely important in certain aspects of molecular electronics.…”

Section: Decoherence and Relaxation (Inelastic Effects)mentioning

confidence: 99%

Molecular electronics: Some views on transport junctions and beyond

Joachim

Ratner

2005

Proc. Natl. Acad. Sci. U.S.A.

502

360

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The field of molecular electronics comprises a fundamental set of issues concerning the electronic response of molecules as parts of a mesoscopic structure and a technology-facing area of science. We will overview some important aspects of these subfields. The most advanced ideas in the field involve the use of molecules as individual logic or memory units and are broadly based on using the quantum state space of the molecule. Current work in molecular electronics usually addresses molecular junction transport, where the molecule acts as a barrier for incoming electrons: This is the fundamental Landauer idea of ''conduction as scattering'' generalized to molecular junction structures. Another point of view in terms of superexchange as a guiding mechanism for coherent electron transfer through the molecular bridge is discussed. Molecules generally exhibit relatively strong vibronic coupling. The last section of this overview focuses on vibronic effects, including inelastic electron tunneling spectroscopy, hysteresis in junction charge transport, and negative differential resistance in molecular transport junctions.

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Section: Decoherence and Relaxation (Inelastic Effects)mentioning

confidence: 99%

Molecular electronics: Some views on transport junctions and beyond

Joachim

Ratner

2005

Proc. Natl. Acad. Sci. U.S.A.

502

360

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“…Molecular long-range electron transfer (ET) in solid phases or liquid solution, in which the ET distance exceeds the structural extension of the donor and acceptor, has been in focus over the last decade and a half (1)(2)(3)(4)(5). Progress has rested on synthetic donor-acceptor molecules (1-3), metalloproteins (2,4,6,7), and on new electrochemical systems in which electrons are brought to tunnel across well characterized, self-assembled films (8,9).…”

mentioning

confidence: 99%

“…In situ STM of redox metalloproteins, with low-lying intermediate transition metal redox levels, holds new perspectives for long-range ET in metalloproteins and for conductivity changes induced by substrate binding such as that observed, for example, for the four-copper redox enzyme, ascorbate oxidase, in aqueous solution (57). The perspectives would extend to the elusive distinction between superexchange, coherent, and sequential ET mechanisms often discussed in ET science (1)(2)(3)(4)(5)(6)(7). Such data are not available presently but are in demand in view of the subtleties associated with the potential control and distribution in the gap region and with problems associated with robust layer configurations for electron exchange between metallic electrodes and adsorbed proteins (58).…”

mentioning

confidence: 99%

An approach to long-range electron transfer mechanisms in metalloproteins: In situ scanning tunneling microscopy with submolecular resolution

Friis

Andersen

Kharkats

et al. 1999

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

131

106

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In situ scanning tunneling microscopy (STM) of redox molecules, in aqueous solution, shows interesting analogies and differences compared with interfacial electrochemical electron transfer ( Molecular long-range electron transfer (ET) in solid phases or liquid solution, in which the ET distance exceeds the structural extension of the donor and acceptor, has been in focus over the last decade and a half (1-5). Progress has rested on synthetic donor-acceptor molecules (1-3), metalloproteins (2, 4, 6, 7), and on new electrochemical systems in which electrons are brought to tunnel across well characterized, self-assembled films (8, 9). These achievements have prompted new theoretical efforts with notions such as directional tunneling along chemical bond networks (10), fluctuating tunnel barriers (11, 12), coherent and resonance ET (13), and self-consistent electronic-vibrational interaction (11).In a parallel development, scanning tunneling and atomic force microscopy (STM and AFM, respectively) have opened exciting new perspectives for mapping molecular adsorbate patterns (14, 15). The primary basis for adsorption patterns in vacuum or air is imaging of small and intermediate-size adsorbate molecules with molecular and submolecular resolution (14-17), combined with theoretical frames for tunneling through adsorbate molecules based on different methodologies (17-21). There are also reported experimental approaches to functional mapping of intermediate-size molecules, most prominently in the form of correlations between the tunnel current and the bias voltage. Target adsorbates for ex situ STM imaging have been, for example, benzene (22, 23), methylazulenes (17, 24), C 60 (25), alkyl and aryl thiolates (17,21,(26)(27)(28), and transition metal phthalocyanins (29) on highly oriented pyrolytic graphite or crystalline surfaces of electronically ''soft'' metals compatible with the adsorbates. STM imaging at the solid͞air interface to molecular and occasionally submolecular resolution also has been extended to biological macromolecules including DNA (30) and a number of redox and nonredox proteins (for an overview, see ref. 31). Functional properties addressed particularly have been the electrical potential distribution and conductivity patterns of the tunnel gap (21, 27-29), resonance tunneling via suitable highest occupied molecular orbitals, lowest unoccupied molecular orbitals, or (transition metal) redox levels (17-21), and the notion of orbital-specific mediation of the tunnel current (29).Combination of STM with concepts of long-range ET in chemical and, particularly, metalloprotein systems must, however, give explicit attention to the fact that the natural medium for most chemical and biological reactivity is aqueous solution. Extension of STM͞AFM to aqueous solution (in situ STM͞ AFM) is established (32, 33) but has raised issues related to adsorbate immobilization, ultrapure solutions, tip coating, independent tip and substrate potential control (32-34), and the fundamental STM and AFM phenomena. In situ...

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“…(8)]. D aw @ 1/t L ,w ird [16][17][18] Es gibt eine reichhaltige Literatur über nichtadiabatischen Elektronentransfer:d er Effekt der Umgebung und des Elektrodenpotentials auf die Stärke V der Wechselwirkung, [19,20] die Entfernungsabhängigkeit von V, [21] Elektronentransfer entlang von Kettenmolekülen, [21,22] aber diese Themen liegen außerhalb unseres Interesses.E infache Elektronentransferprozesse an Metallelektroden in der äußeren Sphäre verlaufen adiabatisch ebenso wie alle elektrokatalytischen Reaktionen. Allenfalls an Elektroden aus Modifikationen von Kohlenstoff wie Graphit, Graphen oder Kohlenstoff-Nanorçhren kçnnte nichtadiabatisches Verhalten auftreten.…”

Section: Elektronentransfer In Der äUßeren Sphäreunclassified

Der präexponentielle Faktor in der Elektrochemie

Chen

Santos

et al. 2018

Angewandte Chemie

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Wie in vielen Zweigen der Wissenschaft, um nicht von der Kultur im Allgemeinen zu reden, so gibt es auch in der Elektrochemie eine Reihe von wiederkehrenden Themen: Forschungsgebiete, die eine Zeit lang populär sind, dann verblassen, wenn ihre Möglichkeiten erschöpft scheinen, um Jahrzehnte später wieder aktuell zu werden, wenn Fortschritte in experimentellen oder theoretischen Techniken neue Forschungsmöglichkeiten eröffnen. Ein gutes Beispiel sind Brennstoffzellen, die fünf solcher Zyklen durchlaufen haben; aber hier soll ein allgemeineres Konzept der Kinetik diskutiert werden, nämlich der präexponentielle Faktor einer Geschwindigkeitskonstanten, der bisher zwei solcher Zyklen durchlaufen hat. Der erste Zyklus umfasst etwa die Zeitspanne 1950 bis 1980, als die Methoden der elektrochemischen Kinetik entwickelt wurden und die Interpretationen auf der Theorie des Übergangszustands basierten. Der zweite wurde durch die Wiederentdeckung der Kramers‐Theorie für Reaktionen in kondensierten Phasen ausgelöst. Dieser Kurzaufsatz soll zeigen, dass es Zeit für einen dritten Zyklus ist, der auf neuen Ergebnissen in der Elektrokatalyse beruht.

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A semiclassical theory of electron transfer reactions in Condon approximation and beyond

Cited by 44 publications

References 21 publications

Molecular electronics: Some views on transport junctions and beyond

Molecular electronics: Some views on transport junctions and beyond

An approach to long-range electron transfer mechanisms in metalloproteins: In situ scanning tunneling microscopy with submolecular resolution

Der präexponentielle Faktor in der Elektrochemie

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