Reaction Rate Maxima at Large Distances between Reactants

Kuss‐Petermann, Martin; Wenger, Oliver S.

doi:10.2533/chimia.2016.177

Cited by 3 publications

(4 citation statements)

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“…The dielectric continuum model based on spherical donors and acceptors with radii of 4 Å predicts an increase in λ of ca. 0.3 eV for CH 3 CN solvent, ,,− but the experimentally observed effect is larger (0.5–0.6 eV). However, it has been noted earlier that dielectric continuum models tend to underestimate the increase of the distance-dependent outer-sphere reorganization energy (λ 0 ), and such models cannot be expected to give an accurate quantitative description of our triads.…”

Section: Resultsmentioning

confidence: 99%

“…In summary, our study shows that electron transfer rates can either increase or decrease with increasing donor-acceptor distance, in clear contrast to the common belief that reaction rates always get slower when the distance between individual reactants increases. 43 This counter-intuitive behavior is readily understandable in the framework of Marcus theory, as pointed out in two early theory papers, 38,39 yet this does not seem to be nearly as widely known as the inverted driving-force effect. The present study is the first systematic investigation of the distance dependence of k ET as a function of driving-force, geared at testing these early theoretical predictions.…”

Section: Discussionmentioning

confidence: 99%

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Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces

Neumann

Wenger

2018

Inorg. Chem.

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The distance dependences of electron transfer rates (k ET) in three homologous series of donor-bridge-acceptor compounds with reaction free energies (G ET 0) of ca.-1.2,-1.6, and-2.0 eV for thermal charge recombination after initial photoinduced charge-separation were studied by transient absorption spectroscopy. In the series with low driving-force, the distance dependence is normal and k ET decreases upon donoracceptor distance (r DA) elongation. In the two series with higher driving-forces, k ET increases with increasing distance over a certain range. This counter-intuitive behavior can be explained by a weakly distance dependent electronic donor-acceptor coupling (H DA) in combination with an increasing reorganization energy (). Our study shows that highly exergonic electron transfers can have distance dependences that differ drastically from those of the more commonly investigated weakly exergonic reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces

Neumann

Wenger

2018

Inorg. Chem.

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“…1b can be calculated as a function of r DA using eqn (1)-(4). 17 For spherical donors and acceptors with radii (a 1 , a 2 ) of 4 Å in CH 3 CN (Z = 1.3341, D s = 35.7) at 298 K, we assumed H (0) DA = 200 cm À1 , b = 0.8 Å À1 , and l i = 0.1 eV. The Marcus parabola obtained for r DA = 8,11,and 21 Å are shown in Fig.…”

Section: Consequences Of Opposing Distance Dependences Of H Da and K Omentioning

confidence: 99%

Unusual distance dependences of electron transfer rates

Kuss‐Petermann

Wenger

2016

Phys. Chem. Chem. Phys.

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Usually the rates for electron transfer (kET) decrease with increasing donor-acceptor distance, but Marcus theory predicts a regime in which kET is expected to increase when the transfer distance gets longer. Until recently, experimental evidence for such counter-intuitive behavior had been very limited, and consequently this effect is much less well-known than the Gaussian free energy dependence of electron transfer rates leading to the so-called inverted driving-force effect. This article presents the theoretical concepts that lead to the prediction of electron transfer rate maxima at large donor-acceptor distances, and it discusses conditions that are expected to favor experimental observations of such behavior. It continues with a consideration of specific recent examples in which electron transfer rates were observed to increase with increasing donor-acceptor distance, and it closes with a discussion of the importance of this effect in the context of light-to-chemical energy conversion.

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“…The reorganization energy depends on the distance between the donor and acceptor (r DA ) and the solvent polarity (Eq. ( 2)) [51][52][53] :…”

Section: Screening Single Atom Catalystsmentioning

confidence: 99%

Understanding the charge transfer effects of single atoms for boosting the performance of Na-S batteries

Lei,

Lu,

Yoshikawa

et al. 2024

Nat Commun

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The effective flow of electrons through bulk electrodes is crucial for achieving high-performance batteries, although the poor conductivity of homocyclic sulfur molecules results in high barriers against the passage of electrons through electrode structures. This phenomenon causes incomplete reactions and the formation of metastable products. To enhance the performance of the electrode, it is important to place substitutable electrification units to accelerate the cleavage of sulfur molecules and increase the selectivity of stable products during charging and discharging. Herein, we develop a single-atom-charging strategy to address the electron transport issues in bulk sulfur electrodes. The establishment of the synergistic interaction between the adsorption model and electronic transfer helps us achieve a high level of selectivity towards the desirable short-chain sodium polysulfides during the practical battery test. These finding indicates that the atomic manganese sites have an enhanced ability to capture and donate electrons. Additionally, the charge transfer process facilitates the rearrangement of sodium ions, thereby accelerating the kinetics of the sodium ions through the electrostatic force. These combined effects improve pathway selectivity and conversion to stable products during the redox process, leading to superior electrochemical performance for room temperature sodium-sulfur batteries.

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Reaction Rate Maxima at Large Distances between Reactants

Cited by 3 publications

References 20 publications

Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces

Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces

Unusual distance dependences of electron transfer rates

Understanding the charge transfer effects of single atoms for boosting the performance of Na-S batteries

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