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

Nemann, Svenja and Wenger, Oliver S.. (2019) Fundamentally Different Distance Dependences of Electron-Transfer Rates for Low and High Driving Forces. Inorganic Chemistry, 58 (1). pp. 855-860.

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Official URL: https://edoc.unibas.ch/73095/

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Abstract

The distance dependences of electron-transfer rates (kET) in three homologous series of donor–bridge–acceptor compounds with reaction free energies (ΔGET0) 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 kET decreases upon donor–acceptor distance (rDA) elongation. In the two series with higher driving forces, kET increases with increasing distance over a certain range. This counterintuitive behavior can be explained by a weakly distance-dependent electronic donor–acceptor coupling (HDA) in combination with an increasing reorganization energy (λ). 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.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Neumann, Svenja
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0020-1669
e-ISSN:1520-510X
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:10 Dec 2019 11:16
Deposited On:10 Dec 2019 11:16

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