<b>Absorption Spectrum of the Hydrated Electron in Water and in Aqueous Solutions</b>

Hart, Edwin J.; Boag, J. W.

doi:10.1021/ja00880a025

Cited by 733 publications

(536 citation statements)

References 3 publications

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“…By 1960, several facilities had achieved the possibility to perform pulsed electron radiolysis [19], which is the equivalent of flash photolysis in the field of radiation chemistry. The final confirmation of the presence of a solvated electron-through observation of its transient absorption spectrum-by means of pulse radiolysis arose in 1962 from Hart and Boag's experiments [20,21], even if Keene may have observed it first [22]. The authors detected a real transient optical absorption around 700 nm and the analogy of the spectrum to that of the electron in ammonia convinced them that it was the solvated electron [20,21].…”

Section: Water Radiolysis: a Brief Historical Surveymentioning

confidence: 99%

“…The final confirmation of the presence of a solvated electron-through observation of its transient absorption spectrum-by means of pulse radiolysis arose in 1962 from Hart and Boag's experiments [20,21], even if Keene may have observed it first [22]. The authors detected a real transient optical absorption around 700 nm and the analogy of the spectrum to that of the electron in ammonia convinced them that it was the solvated electron [20,21]. It is worth stressing that the presence of the solvated electron had been theoretically invoked by Stein in 1952 [23], by Platzman in 1953 [24] and by Weiss in 1953 [25] and 1960 [26].…”

Section: Water Radiolysis: a Brief Historical Surveymentioning

confidence: 99%

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Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation

Caër

2011

Water

488

309

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Abstract:The radiolysis of water due to ionizing radiation results in the production of electrons, H  atoms,  OH radicals, H 3 O + ions and molecules (dihydrogen H 2 and hydrogen peroxide H 2 O 2 ). A brief history of the development of the understanding of water radiolysis is presented, with a focus on the H 2 production. This H 2 production is strongly modified at oxide surfaces. Different parameters accounting for this behavior are presented.

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Section: Water Radiolysis: a Brief Historical Surveymentioning

confidence: 99%

Section: Water Radiolysis: a Brief Historical Surveymentioning

confidence: 99%

Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation

Caër

2011

Water

488

309

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“…[88][89][90][91][92] The hydrated electron has been known since the early 1960's. 144 Anionic water clusters were first observed mass spectroscopically by…”

Section: General Considerationsmentioning

confidence: 99%

A Drude-model approach to dispersion interactions in dipole-bound anions

Wang¹,

Jordan²

2001

The Journal of Chemical Physics

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A one-electron model potential for calculating the binding energy of an excess electron interacting with polar molecules and their clusters is described. The unique feature of this potential is the treatment of polarization and dispersion effects by means of a Drude model. The approach is tested by calculating the energies for binding an excess electron to HCN, (HCN)2, HNC, and (HNC)2. The model potential results are found to be in good agreement with the predictions of high-level all-electron calculations.

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“…A small subset of Bradforth and co-workers' ultrafast spectral measurements associated with the CTTS excitation of aqueous I -are highlighted in Figure 1b; 53 excitation of the I -CTTS band leads to the rapid (<100 fs) appearance of hydrated electrons with a near-unit quantum yield. 3 The newly ejected electrons are formed out of equilibrium and thermalize on a ∼1 ps time scale; 4 the decay at red wavelengths (Figure 1b, red squares) and the corresponding rise at blue wavelengths (Figure 1b, blue circles) indicate a dynamic spectral blue-shift that reflects the equilibration of the ejected hydrated electron (the equilibrated e H 2 O -spectrum is plotted as the red dashed curve in Figure 1a 54,55 ). A significant fraction of the ejected electrons, which reside in I/e solv -contact pairs, subsequently recombine with their I atom parents on an approximately tens-of-picoseconds time scale.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Charge-Transfer-to-Solvent Dynamics of Iodide in Tetrahydrofuran. 2. Photoinduced Electron Transfer to Counterions in Solution

Bragg

Schwartz

2008

J. Phys. Chem. A

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Although they represent the simplest possible charge-transfer reactions, the charge-transfer-to-solvent (CTTS) dynamics of atomic anions exhibit considerable complexity. For example, the CTTS dynamics of iodide in water are very different from those of sodide (Na -) in tetrahydrofuran (THF), leading to the question of the relative importance of the solvent and solute electronic structures in controlling charge-transfer dynamics. In this work, we address this issue by investigating the CTTS spectroscopy and dynamics of I -in THF, allowing us to make detailed comparisons to the previously studied I -/H 2 O and Na -/THF CTTS systems. Since THF is weakly polar, ion pairing with the counterion can have a substantial impact on the CTTS spectroscopy and dynamics of I -in this solvent. In this study, we have isolated "counterion-free" I -in THF by complexing the Na + counterion with 18-crown-6 ether. Ultrafast pump-probe experiments reveal that THF-solvated electrons (e THF -) appear 380 ( 60 fs following the CTTS excitation of "free" I -in THF. The absorption kinetics are identical at all probe wavelengths, indicating that the ejected electrons appear with no significant dynamic solvation but rather with their equilibrium absorption spectrum. After their initial appearance, ejected electrons do not exhibit any additional dynamics on time scales up to ∼1 ns, indicating that geminate recombination of e THF -with its iodine atom partner does not occur. Competitive electron scavenging measurements demonstrate that the CTTS excited state of I -in THF is quite large and has contact with scavengers that are several nanometers away from the iodide ion. The ejection time and lack of electron solvation observed for I -in THF are similar to what is observed following CTTS excitation of Na -in THF. However, the relatively slow ejection time, the complete lack of dynamic solvation, and the large ejection distance/lack of recombination dynamics are in marked contrast to the CTTS dynamics observed for I -in water, in which fast electron ejection, substantial solvation, and appreciable recombination have been observed. These differences in dynamical behavior can be understood in terms of the presence of preexisting, electropositive cavities in liquid THF that are a natural part of its liquid structure; these cavities provide a mechanism for excited electrons to relocate to places in the liquid that can be nanometers away, explaining the large ejection distance and lack of recombination following the CTTS excitation of I -in THF. We argue that the lack of dynamic solvation observed following CTTS excitation of both I -and Na -in THF is a direct consequence of the fact that little additional relaxation is required once an excited electron nonadiabatically relaxes into one of the preexisting cavities. In contrast, liquid water contains no such cavities, and CTTS excitation of I -in water leads to local electron ejection that involves substantial solvent reorganization.

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Absorption Spectrum of the Hydrated Electron in Water and in Aqueous Solutions

Cited by 733 publications

References 3 publications

Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation

Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation

A Drude-model approach to dispersion interactions in dipole-bound anions

Ultrafast Charge-Transfer-to-Solvent Dynamics of Iodide in Tetrahydrofuran. 2. Photoinduced Electron Transfer to Counterions in Solution

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