Absorption spectrum of the hydrated electron paired with nonreactive metal cations

Bonin, Julien; Lampre, Isabelle; Mostafavi, Mehran

doi:10.1016/j.radphyschem.2005.03.016

Cited by 33 publications

(99 citation statements)

References 45 publications

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“…ThisL iPF 6 -dependentk inetic decay reveals that the electron interacts with the salt. As the Li + /Li atom couple has al ower redoxp otential than the solvated electron, [13] the solvated electron does not reactw ith Li + ions. The most probabler eaction is therefore the anion PF 6 À paired with Li + ,a sd etermined by IR spectroscopy ( Figure 8) at 1mol L À1 LiPF 6 [ Table 1, Eq.…”

Section: Picosecond Pulse Radiolysis Approachmentioning

confidence: 99%

“…According to thee lectronic density of the solute andt he solvent, 6% and 11 %o ft he energy,r espectively,a re then absorbed directly by the solute, leading to the release of fluorine atoms FC,f luoride ions F À and of phosphorus pentafluoride PF 5 [Eqs. (13) and (14), Ta ble 1].L astly,i nm olar concentration of LiPF 6 ,t he transient spectrum ( Figure 1) vanishes rapidly, but no other absorbance arises that could be assignedt oP F 5 …”

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confidence: 99%

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Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales

et al. 2015

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The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li-ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li(+), PF6(-)) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation-matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g). The strong Lewis acid PF5 is also formed. This species then forms various R(1)R(2)R(3) P=O molecules, where R is mainly -F, -OH, and -OC2H5. Substitution reactions take place and oligomers are slowly formed. Similar results were obtained in the ageing of an electrochemical cell filled with the same model solution. This study demonstrates that radiolysis enables a description of the reactivity in LIBs from the picosecond timescale until a few days.

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Section: Picosecond Pulse Radiolysis Approachmentioning

confidence: 99%

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Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales

et al. 2015

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“…Moreover, electrons decay very quickly (a few hundreds of ps), as compared to a few microseconds in bulk water. 54,55 They are quickly trapped in the material, likely by impurities such as Fe 3+ . This interpretation is consistent with the lack of relation between the water content and the kinetics.…”

Section: Picosecond Pulse Radiolysis Experimentsmentioning

confidence: 99%

Reaction mechanisms in swelling clays under ionizing radiation: influence of the water amount and of the nature of the clay mineral

et al. 2017

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International audienceWe have studied the H 2 production under ionizing radiation of water confined in synthetic saponite and montmorillonite as a function of the relative humidity. The H 2 radiolytic yields in the dry systems are very similar to that measured in a non-swelling clay mineral. They are 2–3 times higher with one water layer in the interlayer space, evidencing very efficient energy transfers and efficient recombination reactions due to a high confinement. With two water layers, the H 2 yields decrease as compared to the previous case, but remain higher than in bulk water, proving that recombination reactions of hydrogen atoms are less efficient. Electron paramagnetic resonance measurements evidence that reactivity changes significantly with the number of water layers. Saponite and montmorillonite give similar results, showing that reactivity is driven by the amount of water and that the details of the clay structure play a less important role. Lastly, the behavior of natural vs. synthetic swelling clays is discussed. The presence of impurities, even in small quantities, significantly alters energy transfers and has a positive implication for the geological nuclear waste management

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“…We note that the spectral broadening in the presence of high-concentration metallic salt is still an arguable subject. 39,45,56 Bonin et al 45 and Marbach et al 56 claimed the spectral stability of the absorption spectrum of solvated electrons observed in concentrated salt solutions in water or in mixtures of THF/water by laser photolysis experiments, while Kreitus 39 reported a spectral broadening with increasing LiCl concentration by pulse radiolysis measurements.…”

Section: Resultsmentioning

confidence: 99%

Temperature Effect on the Absorption Spectrum of the Hydrated Electron Paired with a Lithium Cation in Deuterated Water

et al. 2007

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The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO4 deuterated water solutions were measured by pulse radiolysis techniques from room temperature to 300 degrees C at a constant pressure of 25 MPa. The results show that when the temperature is increased and the density is decreased, the absorption spectrum of the electron in the presence of a lithium cation is shifted to lower energies. Quantum classical molecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a lithium cation have been performed to compare with the experimental results. According to the QCMD simulations, the change in the shape of the spectrum is due to one of the three p-like excited states of the solvated electron destabilized by core repulsion. The study of s --> p transition energies for the three p-excited states reveals that for temperatures higher than room temperature, there is a broadening of each individual s --> p absorption band due to a less structured water solvation shell.

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Absorption spectrum of the hydrated electron paired with nonreactive metal cations

Cited by 33 publications

References 45 publications

Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales

Electrolytes Ageing in Lithium‐ion Batteries: A Mechanistic Study from Picosecond to Long Timescales

Reaction mechanisms in swelling clays under ionizing radiation: influence of the water amount and of the nature of the clay mineral

Temperature Effect on the Absorption Spectrum of the Hydrated Electron Paired with a Lithium Cation in Deuterated Water

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