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

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

Geminate recombination of 24 radical anions (M&z.rad; − ) with solvated protons (RH 2 + ) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad; − and RH 2 + together to form intimate (contact and solvent separated) ion pairs, d...

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Veröffentlicht in:Physical chemistry chemical physics : PCCP 2017-12, Vol.19 (48), p.32272-32285
Hauptverfasser: Chen, Hung-Cheng, Cook, Andrew R, Asaoka, Sadayuki, Boschen, Jeffery S, Windus, Theresa L, Miller, John R
Format: Artikel
Sprache:eng
Schlagworte:
Anions
charge delocalization
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ion pair
Ion pairs
ion recombination
Ions
oligofluorenes
Onsager escape
Protons
pulse radiolysis
radiation chemistry
Radiolysis
Rate constants
Tetrahydrofuran
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Zusammenfassung:Geminate recombination of 24 radical anions (M&z.rad; − ) with solvated protons (RH 2 + ) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad; − and RH 2 + together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH 2 + to M&z.rad; − . 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 (
ISSN:1463-9076
1463-9084
DOI:10.1039/c7cp05880b