Topic
Outer sphere electron transfer
About: Outer sphere electron transfer is a research topic. Over the lifetime, 1406 publications have been published within this topic receiving 32472 citations.
Papers published on a yearly basis
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Papers
TL;DR: In this paper, the authors considered electron transfer between biological molecules in terms of a nonadiabatic multiphonon nonradiative decay process in a dense medium and derived an explicit, compact and useful expression for the electron transfer probability.
Abstract: This paper considers electron transfer between biological molecules in terms of a nonadiabatic multiphonon nonradiative decay process in a dense medium. This theoretical approach is analogous to an extended quantum mechanical theory of outer sphere electron transfer processes, incorporating the effects of both low‐frequency medium phonon modes and the high‐frequency molecular modes. An explicit, compact and useful expression for the electron transfer probability is derived, which is valid throughout the entire temperature range, exhibiting a continuous transition from temperature independent tunneling between nuclear potential surfaces at low temperatures to an activated rate expression at high temperatures. This result drastically differs at low temperatures from the common, semiclassical, Gaussian approximation for the transition probability. The experimental data of De Vault and Chance [Biophys. J. 6, 825 (1966)] on the temperature dependence of the rate of electron transfer from cytochrome to the chlorophyll reaction center in the photosynthetic bacterium Chromatium are properly accounted for in terms of the present theory.
1,411 citations
TL;DR: In this article, the authors classified the catalytic cycles for the H2-hydrogenation (H) and transfer hydrogenation (T) of CO and cN bonds catalyzed by over 100 ruthenium hydride complexes in organic and aqueous media.
1,245 citations
801 citations
TL;DR: In this article, various surface modification procedures were used on glassy carbon (GC) electrodes to yield surfaces with low oxide content or which lack specific oxide functional groups, and monolayers of several different adsorbates were formed on GC surfaces before electrochemical evaluation.
Abstract: Various well-established and novel surface modification procedures were used on glassy carbon (GC) electrodes to yield surfaces with low oxide content or which lack specific oxide functional groups. In addition, monolayers of several different adsorbates were formed on GC surfaces before electrochemical evaluation. Both the nonspecific monolayer adsorbates and reagents which chemisorb to specific functional groups were observed on the surface with Raman and photoelectron spectroscopy. The various GC surfaces were then evaluated for their electron transfer reactivity with nine redox systems in aqueous electrolyte, including Ru(NH3)62+/3+, Fe(CN6)3-/4-, ascorbic acid, and Feaq3+/2+. The nine systems were categorized according to their kinetic sensitivity to surface modification. Several, including Ru(NH3)62+/3+, are insensitive to surface modifications and are considered outer sphere. Feaq3+/2+, Vaq2+/3+, and Euaq2+/3+ are catalyzed by surface carbonyl groups and are very sensitive to the removal of surface...
733 citations
TL;DR: In agreement with other workers, it is found that inner sphere complexes form, apparently involving bidentate (bridging) arsenate or arsenite, and this understanding of As mobility in near-surface environments is clarified.
Abstract: The mechanisms whereby As(III) and As(V) in aqueous solution (pH 5.5−6.5) interact with the surfaces of goethite, lepidocrocite, mackinawite, and pyrite have been investigated using As K-edge EXAFS and XANES spectroscopy. Arsenic species retain original oxidation states and occupy similar environments on the oxyhydroxide substrates, with first-shell coordination to four oxygens at 1.78 A for As(III) and 1.69 A for As(V). In agreement with other workers, we find that inner sphere complexes form, apparently involving bidentate (bridging) arsenate or arsenite. Interaction of As(III) and As(V) with the sulfide surfaces shows primary coordination to four oxygens (As−O: 1.69−1.76 A) with further sulfur (∼3.1 A) and iron (3.4−3.5 A) shells suggesting outer sphere complexation. Arsenic species were also coprecipitated with mackinawite (pH 4.0), and these samples were further studied following oxidation. At high As(III) or As(V) concentrations, arsenate or arsenite species form, probably as sorption complexes, al...
498 citations
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Performance Metrics
| Year | Papers |
|---|---|
| 2025 | 2 |
| 2024 | 5 |
| 2023 | 11 |
| 2022 | 14 |
| 2021 | 28 |
| 2020 | 33 |