Investigations of bimolecular photoinduced electron transfer reactions in polar solvents using ultrafast spectroscopy

Vauthey, Eric

doi:10.1016/j.jphotochem.2005.12.019

Cited by 69 publications

(51 citation statements)

References 124 publications

(180 reference statements)

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“…The reader should note that the distant electron-transfer model employed here is not at all in contradiction with the observation of ultrafast charge recombination of the ions, as has been suggested by Vauthey et al [89,90] Indeed, at the large quencher concentration employed by these authors the majority of the ions are formed through static quenching at contact. In fact, the distribution of ions then mirrors the combined effect of the solvent structure and the intrinsic rate with a large portion of ions being generated at contact.…”

Section: Discussioncontrasting

confidence: 46%

The Rehm–Weller Experiment in View of Distant Electron Transfer

Rosspeintner

Kattnig

Angulo

et al. 2008

Chemistry A European J

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The driving-force dependence of bimolecular fluorescence quenching by electron transfer in solution, the Rehm-Weller experiment, is revisited. One of the three long-standing unsolved questions about the features of this experiment is carefully analysed here, that is, is there a diffusional plateau? New experimental quenching rates are compiled for a single electron donor, 2,5-bis(dimethylamino)-1,3-benzenedicarbonitrile, and eighteen electron acceptors in acetonitrile. The data are analysed in the framework of differential encounter theory by using an extended version of the Marcus theory to model the intrinsic electron-transfer step. Only by including the hydrodynamic effect and the solvent structure can the experimental findings be well modelled. The diffusional control region, the "plateau", reveals the inherent distance dependence of the reaction, which is shown to be a general feature of electron transfer in solution.

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Section: Discussioncontrasting

confidence: 46%

The Rehm–Weller Experiment in View of Distant Electron Transfer

Rosspeintner

Kattnig

Angulo

et al. 2008

Chemistry A European J

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“…[45][46] As can be clearly seen in Figures 2 and 3 The two observed components suggest the occurrence of two types of donor-acceptor ion pairs with different associated couplings, in accordance with previous reports on other donor-acceptor systems. [47][48][49][50] The geometry and electronic coupling between donor and acceptor molecules can greatly affect both charge separation and charge recombination rates. 49 Hence, it is expected that the strong electronically coupled ion pairs will undergo fast charge recombination either to the neutral molecule or to the less coupled ion pairs.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

et al. 2015

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“…before a large electronic coupling is achieved. [34][35][36][37][38] This situation favors full charge separation, i.e. the formation of a radical ion pair rather than an exciplex (assuming that D and A are neutral closed-shell species).…”

Section: Introductionmentioning

confidence: 99%

Bimodal Exciplex Formation in Bimolecular Photoinduced Electron Transfer Revealed by Ultrafast Time-Resolved Infrared Absorption

2015

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The dynamics of a moderately exergonic photoinduced charge separation has been investigated by ultrafast time-resolved infrared absorption with the dimethylanthracene/phthalonitrile donor/acceptor pair in solvents covering a broad range of polarity. A distinct spectral signature of an exciplex could be identified in the -C≡N stretching region. On the basis of quantum chemistry calculations, the 4-5 times larger width of this band compared to those of the ions and of the locally excited donor bands is explained by a dynamic distribution of exciplex geometry with different mutual orientations and distances of the constituents and, thus, with varying charge-transfer character. Although spectrally similar, two types of exciplexes could be distinguished by their dynamics: short-lived, "tight", exciplexes generated upon static quenching and longer-lived, "loose", exciplexes formed upon dynamic quenching in parallel with ion pairs. Tight exciplexes were observed in all solvents, except in the least polar diethyl ether where quenching is slower than diffusion. The product distribution of the dynamic quenching depends strongly on the solvent polarity: whereas no significant loose exciplex population could be detected in acetonitrile, both exciplex and ion pair are generated in less polar solvents, with the relative population of exciplex increasing with decreasing solvent polarity. These results are compared with those reported previously with donor/acceptor pairs in different driving force regimes to obtain a comprehensive picture of the role of the exciplexes in bimolecular photoinduced charge separation.

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Investigations of bimolecular photoinduced electron transfer reactions in polar solvents using ultrafast spectroscopy

Cited by 69 publications

References 124 publications

The Rehm–Weller Experiment in View of Distant Electron Transfer

The Rehm–Weller Experiment in View of Distant Electron Transfer

Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

Bimodal Exciplex Formation in Bimolecular Photoinduced Electron Transfer Revealed by Ultrafast Time-Resolved Infrared Absorption

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