Solvated electron in irradiated melts of alkaline halides

Пикaeв, A.К.; Makarov, Igor; Zhukova, T. N.

doi:10.1016/0146-5724(82)90005-x

Cited by 14 publications

(33 citation statements)

References 8 publications

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“…Young estimated ℏω max = 2.25 eV at T = 923 K . Pikaev et al report on spectra of pulse radiolytically produced electrons in LiBr melts (but not in LiCl melts). At T = 873 K they observed ℏω max = 2.48 eV and W 1/2 = 1.50 eV.…”

Section: Resultsmentioning

confidence: 99%

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Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

et al. 1999

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Some years ago I. V. Kreitus measured changes in the optical characteristics of pulse radiolytically generated solvated electrons in solutions of LiCl in H2O and D2O over the LiCl concentration range 0−14.06 M (J. Phys. Chem. 1985, 89, 1987). With increasing LiCl concentration he observed a nonuniform blue-shift of the position of the esolv - absorption maximum and a similar discontinuous increase of the half-width of the absorption band. More rapid changes were observed just in those concentration regions which correspond to the stoichiometric mixtures such as LiCl·6H2O and LiCl·4H2O, respectively. Kreitus asserted that this effect is related to the microstructure of the solutions produced by Li+. He concluded finally that the high sensitivity of the esolv - absorption spectrum to slight microstructural changes in the medium could be used in future as a precise method for investigation of the solution structure. These experimental results and especially their interpretation have far reaching consequences. We therefore felt there is a need to repeat at least some of these measurements very carefully. It became all the more necessary as a femtosecond study on the solvation dynamics of electrons in concentrated aqueous LiCl solutions was interpreted according to the results of Kreitus. We report on our experimental results which neither corroborate the experimental data of Kreitus nor support his theoretical conclusions.

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Section: Resultsmentioning

confidence: 99%

“…Within the experimental error these results are independent of the LiCl concentration. Pikaev et al mentioned absorption bands for an aqueous solution of 10 -3 M potassium iodide alone at 1.71 and 3.31 eV with a half-width W 1/2 = 0.8 eV for the high energy band. The corresponding ratio of the extinction coefficients was given as 3.7.…”

Section: Methodsmentioning

confidence: 99%

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

et al. 1999

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“…The hydrated electron has long been considered a distinct chemical species of relevance to many branches of chemistry. − As the most elementary reducing agent and the simplest “hydrated ion”, it has established itself as a unique curiosity among both chemists and physicists, providing a testing ground for theories of chemical reactivity and solvation. Since its original discovery, it has been most closely connected with the radiation chemistry of aqueous solutions where ionization, by radiolysis or photolysis, can lead to the production of a solvated electron. In the absence of an acceptor of sufficient electron affinity, the electron may diffuse through the solvent medium by exploiting solvent fluctuations.…”

Section: Introductionmentioning

confidence: 99%

Hydrated Electron Diffusion: The Importance of Hydrogen-Bond Dynamics

Tay

Boutin

2009

J. Phys. Chem. B

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Mixed quantum-classical molecular dynamics simulations have been used to investigate hydrated electron diffusion within the temperature range 283-400 K. The Arrhenius to non-Arrhenius behavior observed in experiments is reproduced with a transition temperature, T(t), estimated at 320 K. Above this temperature, the activation energy for diffusion is 7.5 +/- 0.3 kJ mol(-1). By computing equilibrium constants for interconversions between H-bonded and non-H-bonded configurations, we show that hydrated electron diffusion is driven by fluctuations in the H-bond network of hydrating water molecules. The computed activation energy is in fact the energy change associated with H-bond breakings. Above T(t), librational dynamics appear to dominate H-bond breakings in hydrating water molecules. Below T(t), in the non-Arrhenius region, hydrated electron diffusion is driven by both the librational and translational dynamics of the hydrating water molecules. A kinetic analysis is presented to complement the above findings.

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“…In summary, our results provide an EPR evidence for physical trapping of excess electron in IL P 14 NTf 2 at 77 K. The resulting species is sensitive to the near IR light, which may suggest its similarity to a solvated electron found in time-resolved optical absorption studies at room temperature. − Also, it may be compared to solvated electrons in molten inorganic salts known from pulse radiolysis studies. , Even though the yield of trapped electrons revealed by EPR is low, this result appears to be of basic significance, in view of conflicting previous findings.…”

mentioning

confidence: 50%

“…2−4 Also, it may be compared to solvated electrons in molten inorganic salts known from pulse radiolysis studies. 27,28 Even though the yield of trapped electrons revealed by EPR is low, this result appears to be of basic significance, in view of conflicting previous findings.…”

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confidence: 69%

EPR Evidence for a Physically Trapped Excess Electron in a Glassy Ionic Liquid

Saenko

Takahashi

Feldman

2013

J. Phys. Chem. Lett.

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The fate of excess electron produced in room temperature ionic liquids is an attractive and important topic, and its kinetics and optical absorption spectrum have been studied using pulse radiolysis and laser photolysis. However, there has been no clear evidence for existence of the solvated electron in EPR experiments. Here we report that an EPR spectrum of irradiated glassy pyrrolidinium-based ionic liquid at 77 K reveals a sharp singlet signal (line width of 0.47 mT), which can be attributed to a physically trapped (solvated) electron. The EPR signal shows easy microwave power saturation and is effectively bleached with red light (>600 nm). The present results have important implications for the characterization of trapped or solvated electrons in ionic liquids and better understanding of their structure and reactivity.

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Solvated electron in irradiated melts of alkaline halides

Cited by 14 publications

References 8 publications

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Hydrated Electron Diffusion: The Importance of Hydrogen-Bond Dynamics

EPR Evidence for a Physically Trapped Excess Electron in a Glassy Ionic Liquid

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Solvated electron in irradiated melts of alkaline halides

Cited by 14 publications

References 8 publications

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H2O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H2O Solutions?

Hydrated Electron Diffusion: The Importance of Hydrogen-Bond Dynamics

EPR Evidence for a Physically Trapped Excess Electron in a Glassy Ionic Liquid

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Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?

Is There Any Effect of Solution Microstructure on the Solvated Electron Absorption Spectrum in LiCl/H₂O Solutions?