Escape of anions from geminate recombination in THF due to charge delocalization

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2017-01-01
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Chen, Hung-Cheng
Cook, Andrew
Asaoka, Sadayuki
Boschen, Jeffrey
Windus, Theresa
Miller, John
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Windus, Theresa
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Ames National LaboratoryChemistry
Abstract

Geminate recombination of 24 radical anions (M˙−) with solvated protons (RH2+) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M˙− and RH2+ together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH2+ to M˙−. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (

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