Estimated Distribution Functions of Electronic Redox Levels and the Rate of Chemical Reactions of Excess Electrons in Dielectric Liquids

Henglein, A.

doi:10.1002/bbpc.19750790205

Cited by 31 publications

(4 citation statements)

References 31 publications

(6 reference statements)

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“…Other pulse radiolysis data in the chemical field includes: Brocklehurst (1973), Brocklehurst, Bull & Evans (1975), Miller (1972Miller ( , 1973Miller ( , 1975, Miller & Willard (1972), Buxton & Kemsley (1976), Henglein (1974Henglein ( , 1975, Gratzel, Henglein & Janata (1975) and Frank et al (1976). Reviews have been written by Brocklehurst (1979), Hart & Anbar (1970), Rice & Pilling (1978), Hunt (1976), Kevan (1974), and a conference on 'Electrons in Fluids' (Proceedings, 1977).…”

Section: (E) Pulse Radiolysismentioning

confidence: 99%

Quantum mechanical tunnelling in biological systems

DeVault

1980

Quart. Rev. Biophys.

329

187

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‘Tunnelling’ is the metaphorical name given to the process, possible in quantum mechanics, but not in classical mechanics, whereby a particle can disappear from one side of a potential-energy barrier and appear on the other side without having enough kinetic energy to mount the barrier. One can think of this as a manifestation of the wave-nature of particles. The wavelength is larger if a particle is lighter. In particular electrons, being very light compared to atoms, have wavelengths as large or larger than atoms at energies found in the valence shells of molecules. Thus, they easily ooze through and around atoms and molecules. We are also concerned with the tunnelling of heavy particles: nuclei, atoms, molecules.

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Section: (E) Pulse Radiolysismentioning

confidence: 99%

Quantum mechanical tunnelling in biological systems

DeVault

1980

Quart. Rev. Biophys.

329

187

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“…That is not the case for electron attachment to BQ which has a negative temperature coefficient in TMS . It was suggested early on by Henglein , that the concepts of electron transfer in solution be applied to solvated electron attachment reactions. Here we follow this path applying theories of electron transfer − cast in forms we discussed earlier .…”

Section: Discussionmentioning

confidence: 99%

“…The observation that rates are well below the diffusion limit of eq 3 in high mobility liquids has been attributed to the fact that the residence time, τ D = R e 2 / 2D, of an electron within a reaction radius is short compared to the attachment time τ A in contact. 26 Thus, for high mobility liquids, rate constants tend to level off at a value below the diffusion limit, defined by eq 3 with R e = 0.72 nm. 26,27 In TMS where μ D = 100 cm 2 /Vs, one finds τ D = R e 2 /2D ∼ 1 fs; similarly, τ D ∼ 15 fs in 2,2,4-TMP with ∼15 times lower drift mobility.…”

Section: Bqmentioning

confidence: 99%

“…26 Thus, for high mobility liquids, rate constants tend to level off at a value below the diffusion limit, defined by eq 3 with R e = 0.72 nm. 26,27 In TMS where μ D = 100 cm 2 /Vs, one finds τ D = R e 2 /2D ∼ 1 fs; similarly, τ D ∼ 15 fs in 2,2,4-TMP with ∼15 times lower drift mobility. Thus, the picture 26,27 of eq 4 estimates that the rate of electron transfer in contact >10 15 s −1 is needed to obtain the diffusion controlled limit.…”

Section: Bqmentioning

confidence: 99%

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Pressure Tuning of Electron Attachment to Benzoquinones in Nonpolar Fluids: Continuous Adjustment of Free Energy Changes

et al. 2014

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Changing pressure from 1 to 2500 bar continuously tunes free energy changes for electron attachment to molecules in nonpolar liquids by nearly 0.3 eV. Rate constants for electron attachment to substituted benzoquinones were determined over an extended free energy range of nearly 1 eV by a combination of solute, pressure, temperature, and use of solvents with differing energies of the quasifree electron, V 0 : tetramethylsilane (TMS) and 2,2,4-trimethylpentane (TMP). The rates of attachment to both benzoquinone (BQ) and 2,5-dichlorobenzoquinone in TMS increase as the pressure increases to 2500 bar, while in TMP the rates are higher but change little with pressure; the rate of attachment to fluoranil in TMS is similarly high at 1 bar but decreases with increasing pressure. Together the observed rate constants can be qualitatively interpreted to yield a rate vs free energy relation having both normal and Marcus inverted region behavior. Because the electron attachment reactions yield excited states, quantitative interpretation of the free energy dependence requires knowledge of the excited state energies. The electron enters the second lowest π* orbital to form a π*−π* excited state, which quickly relaxes to the lower n−π* excited state. The rate of attachment to this excited state is low when the free energy of reaction, ΔG°, is positive and increases as ΔG°decreases until near −0.2 eV, after which the rate decreases. While excited state energies are uncertain, reasonable estimates are obtained from absorption, excitation, and fluorescence spectra of the product radical anions measured here. The results are modeled using Marcus theory with inclusion of a high frequency molecular vibration.

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Physikalische und chemische Eigenschaften gelöster Elektronen (Überschußelektronen)

Schindewolf¹

1978

Angew. Chem.

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Estimated Distribution Functions of Electronic Redox Levels and the Rate of Chemical Reactions of Excess Electrons in Dielectric Liquids

Cited by 31 publications

References 31 publications

Quantum mechanical tunnelling in biological systems

Quantum mechanical tunnelling in biological systems

Pressure Tuning of Electron Attachment to Benzoquinones in Nonpolar Fluids: Continuous Adjustment of Free Energy Changes

Physikalische und chemische Eigenschaften gelöster Elektronen (Überschußelektronen)

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