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• W2050591010 abstract "The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by other factors that alter the solution environment local to the CTTS anion, including the presence of cosolutes, cosolvents, and other ions. In this paper, we examine the ultrafast CTTS dynamics of iodide in liquid tetrahydrofuran (THF) with a particular focus on how the solvent dynamics and the CTTS electron-ejection process are altered in the presence of various counterions. In weakly polar solvents such as THF, iodide salts can be strongly ion-paired in solution; the steady-state UV−visible absorption spectroscopy of various iodide salts in liquid THF indicates that the degree of ion-pairing changes from strong to weak to none as the counterion is switched from Na+ to tetrabutylammonium (t-BA+) to crown-ether-complexed Na+, respectively. In our ultrafast experiments, we have excited the I- CTTS transition of these various iodide salts at 263 nm and probed the dynamics of the CTTS-detached electrons throughout the visible and near-IR. In the previous paper of this series (Bragg, A. E.; Schwartz, B. J. J. Phys. Chem. B 2008, 112, 483−494), we found that for “counterion-free” I- (obtained by complexing Na+ with a crown ether) the CTTS electrons were ejected ∼6 nm from their partner iodine atoms, the result of significant nonadiabatic coupling between the CTTS excited state and extended electronic states supported by the naturally existing solvent cavities in liquid THF, which also serve as pre-existing electron traps. In contrast, for the highly ion-paired NaI/THF system, we find that ∼90% of the CTTS electrons are “captured” by a nearby Na+ to form (Na+, e-)THF “tight-contact pairs” (TCPs), which are chemically and spectroscopically distinct from both solvated neutral sodium atoms and free solvated electrons. A simple kinetic model is able to reproduce the details of the electron capture process, with 63% of the electrons captured quickly in ∼2.3 ps, 26% captured diffusively in ∼63 ps, and the remaining 11% escaping out into the solution on subnanosecond time scales. We also find that the majority of the CTTS electrons are ejected to within 1 or 2 nm of the Na+. This demonstrates that the presence of the nearby cation biases the relocalization of CTTS-generated electrons from I- in THF, changing the nonadiabatic coupling to the extended, cavity-supported electronic states in THF to produce a much tighter distribution of electron-ejection distances. In the case of the more loosely ion-paired t-BA+−I-/THF system, we find that only 10−15% of the CTTS-ejected electrons associate with t-BA+ to form “loose-contact pairs” (LCPs), which are characterized by a much weaker interaction between the electron and cation than occurs in TCPs. The formation of (t-BA+, e-)THF LCPs is characterized by a Coulombically induced blue shift of the freespectrum on a ∼5-ps time scale. We argue that the weaker interaction between t-BA+ and the parent I- results in little change to the CTTS-ejection process, so that only those electrons that happen to localize in the vicinity of t-BA+ are captured to form LCPs. Finally, we interpret the correlation between electron capture yield and counterion-induced perturbation of the I- CTTS transition as arising from changes in the distribution of ion-pair separations with cation identity, and we discuss our results in the context of relevant solution conductivity measurements." @default.
• W2050591010 created "2016-06-24" @default.
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• W2050591010 date "2008-04-01" @default.
• W2050591010 modified "2023-09-23" @default.
• W2050591010 title "Ultrafast Charge-Transfer-to-Solvent Dynamics of Iodide in Tetrahydrofuran. 2. Photoinduced Electron Transfer to Counterions in Solution" @default.
• W2050591010 cites W1964464437 @default.
• W2050591010 cites W1965434561 @default.
• W2050591010 cites W1968236293 @default.
• W2050591010 cites W1968789039 @default.
• W2050591010 cites W1968838342 @default.
• W2050591010 cites W1971420380 @default.
• W2050591010 cites W1979207323 @default.
• W2050591010 cites W1981908415 @default.
• W2050591010 cites W1986174964 @default.
• W2050591010 cites W1986910417 @default.
• W2050591010 cites W1987765885 @default.
• W2050591010 cites W1988289871 @default.
• W2050591010 cites W1991687043 @default.
• W2050591010 cites W1993489077 @default.
• W2050591010 cites W1995267105 @default.
• W2050591010 cites W1997093520 @default.
• W2050591010 cites W1997164257 @default.
• W2050591010 cites W1998031139 @default.
• W2050591010 cites W1999580556 @default.
• W2050591010 cites W2006895805 @default.
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• W2050591010 cites W2019172414 @default.
• W2050591010 cites W2023310100 @default.
• W2050591010 cites W2027027575 @default.
• W2050591010 cites W2036706782 @default.
• W2050591010 cites W2038367157 @default.
• W2050591010 cites W2040143919 @default.
• W2050591010 cites W2041057937 @default.
• W2050591010 cites W2049740484 @default.
• W2050591010 cites W2053101039 @default.
• W2050591010 cites W2056141570 @default.
• W2050591010 cites W2057049368 @default.
• W2050591010 cites W2062378328 @default.
• W2050591010 cites W2062949678 @default.
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• W2050591010 cites W2074451902 @default.
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• W2050591010 cites W2075022765 @default.
• W2050591010 cites W2078410271 @default.
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• W2050591010 cites W2151767184 @default.
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• W2050591010 doi "https://doi.org/10.1021/jp712039u" @default.
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