Application of the photoinduced electron transfer model to the hydrated-electron spectrum

Hug, Gordon L.; Carmichael, Ian

doi:10.1021/j100214a029

Cited by 2 publications

(1 citation statement)

References 12 publications

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“…It is interesting to contemplate whether this realization would have made a difference in the long-running debate concerning the “cavity” vs “solvent anion” nature of hydrated electrons, if the correct extinction coefficient had been reported in the 1960s. Virtually every model of solvated electron which has ever been presented was justified by its ability to reproduce the optical absorption spectrum, ,,,,, but a cavity model, or a modern single electron/pseudopotential model, clearly cannot produce oscillator strength greater than unity. The result reinforces the arguments recently presented by Shkrob and co-workers on the basis of the magnetic resonance evidence, , that all solvated electrons, even in water, should really be viewed as multimer-solvent anions.…”

Section: Discussionmentioning

confidence: 99%

Solvated Electron Extinction Coefficient and Oscillator Strength in High Temperature Water

et al. 2010

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The decadic extinction coefficient of the hydrated electron is reported for the absorption maximum from room temperature to 380 degrees C. The extinction coefficient is established by relating the transient absorption of the hydrated electrons in the presence of a scavenger to the concentration of stable product produced in the same experiment. Scavengers used in this report are SF(6,) N(2)O, and methyl viologen. The room temperature value is established as 22,500 M(-1) cm(-1), higher by 10-20% than values used over the last several decades. We demonstrate how previous workers arrived at a low value by incorrect choice of a radiolysis yield value. With this revision, the integrated oscillator strength, corrected by refractive index, is definitely (ca. 10%) larger than unity. This result is fully consistent with EPR and resonance Raman results which indicate mixing of the hydrated electron wave function with solvent electronic orbitals. Oscillator strength appears to be conserved vs temperature.

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Section: Discussionmentioning

confidence: 99%

Solvated Electron Extinction Coefficient and Oscillator Strength in High Temperature Water

et al. 2010

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An ESR study on solvated electrons in water and alcohols: Difference in the g factor and related analysis of the electronic state by MO calculation

Shiraishi

Ishigure

Morokuma

1988

The Journal of Chemical Physics

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An induction-detecting ESR spectrometer system, capable of μs time resolution, has been set up, and measurements were made on the radiolytically produced solvated electrons in water, methanol, ethanol, and mixtures of water and these alcohols. The spectrum of the solvated electron was a singlet in all these solvents. The g factor of the hydrated electron was measured to be 2.000 47±0.000 07 at 22 °C in reasonable agreement with the reported data. While this value is significantly smaller than the free electron g factor, the corresponding g factors in methanol and in ethanol, respectively 2.002 05±0.000 07 and 2.001 97±0.000 07 at 22 °C, were found much closer to it. In both methanol–water and ethanol–water mixtures the g factor of the solvated electron varied approximately in proportion to the mole fraction. The g shift of the hydrated electron was interpreted as arising from spin density in the proximity of oxygen nuclei of water molecules. Ab initio MO calculations were performed for an anionic cluster of water and that of methanol, assuming a cavity-like structure. The result showed that while in a water cluster the spin population on oxygen 2p atomic orbitals was in fact significant, the corresponding orbital spin population was smaller in a methanol cluster especially with a dipole-oriented model. The difference was considered to be related to increased diffuseness of the half-occupied orbital in the latter cluster.

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Application of the photoinduced electron transfer model to the hydrated-electron spectrum

Cited by 2 publications

References 12 publications

Solvated Electron Extinction Coefficient and Oscillator Strength in High Temperature Water

Solvated Electron Extinction Coefficient and Oscillator Strength in High Temperature Water

An ESR study on solvated electrons in water and alcohols: Difference in the g factor and related analysis of the electronic state by MO calculation

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