Novel Precursors of Solvated Electrons in Water: Evidence for a Charge Transfer Process

Laenen, R.; Roth, Thomas; Laubereau, A.

doi:10.1103/physrevlett.85.50

Cited by 172 publications

(186 citation statements)

References 16 publications

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“…That is, it leaves our THz observation window after ≈200 fs (Fig. 1), then appears in the mid-IR [9-11, 23, 24] and eventually the NIR spectral range upon full solvation [10,14,24]. Afterwards, the hydrated electron recombines in a diffusive process on a much slower timescale (Fig.…”

Section: Discussionmentioning

confidence: 99%

“…According to a simple particle-in-a-box picture, such a localization should be accompanied by a shift in the absorption spectrum from potentially the THz or even GHz regions over the mid-IR to the VIS spectral range. The latter stages of this process have indeed been observed by femtosecond pump-probe experiments in the mid-IR [9-11, 23, 24] or NIR/VIS regime [10,14,24], but the initial frequency at which this process starts, which is directly related to the initial degree of delocalization of the excess electron, has not yet been explored.…”

mentioning

confidence: 97%

“…To appreciate the system in full, it is vital to understand the initial steps from the photodetachment to the e − aq formation. Femtosecond pump-probe experiments have been used to unravel details of the equilibration processes following the trapping by the solvent [5][6][7][8][9][10][11][12]. In addition, picosecond measurements on the recombination kinetics of e − aq have described the ejected electron's migration lengths from its geminate partners [13][14][15][16][17][18][19][20][21][22].…”

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confidence: 99%

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Direct observation of the collapse of the delocalized excess electron in water

et al. 2014

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It is generally assumed that the hydrated electron occupies a quasi-spherical cavity surrounded by only a few water molecules in its equilibrated state. However, in the very moment of its generation, before water has had time to respond to the extra charge, it is expected to be significantly larger in size. According to a particle-in-a-box picture, the frequency of its absorption spectrum is a sensitive measure of the initial size of the electronic wavefunction. Here, using transient terahertz spectroscopy, we show that the excess electron initially absorbs in the far-infrared at a frequency for which accompanying ab initio molecular dynamics simulations estimate an initial delocalization length of 40 Å. The electron subsequently shrinks due to solvation and thereby leaves the terahertz observation window very quickly, within 200 fs.

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Section: Discussionmentioning

confidence: 99%

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Direct observation of the collapse of the delocalized excess electron in water

et al. 2014

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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%

“…Reactions involving electrons in bulk water are of fundamental importance in radiation chemistry, electrochemistry and biology. [88][89][90][91][92] Yet, even the nature of an excess electron in bulk water remains controversial. [93][94][95][96][97][98][99][100][101][102][103] Although the long-held view is that an excess electron in bulk water is trapped in an approximately spherical cavity, [104][105][106][107] giving the so-called hydrated electron, Domcke and coworkers have proposed that the excess electron is actually associated with a H 3 O species.…”

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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Electron Dynamics at Polar Molecule–Metal Interfaces: Competition between Localization, Solvation, and Transfer

Stähler

Bovensiepen

Wolf

2010

Dynamics at Solid State Surfaces and Interfaces

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Electron-induced processes and reactions in aqueous systems are of key relevance in diverse fields, ranging from electron transfer and light harvesting in biological systems, photochemistry in the atmosphere, electrochemistry and corrosion, radiation chemistry, and nuclear waste remediation to medical diagnosis and therapy [1][2][3]. These processes usually involve the creation, rearrangement, and transfer of electrons or charged particles in a polar environment. Therefore, solvation and localization of these charges by the reorientation of the surrounding molecular dipoles are key processes that govern the dynamics and reaction rates in aqueous systems or other polar solvents. The solvation reorganization energy, which is associated with the polarization of the solvent environment, determines the energetics and stabilization of charged particles in the solvent. Its magnitude is on the order of several eV [4] and providesfacilitated by thermal fluctuations of the solvent environmentthe driving force for electron transfer in solution. Electron transfer can therefore take place spontaneously at room temperature, as described by Marcus theory [5]. On the other hand, if an excess charge or dipole is suddenly created in a polar solvent (e.g., by photoexcitation), its environment will respond on ultrafast timescales, which are characteristic of the molecular rearrangements of the solvent [6]. In bulk liquid water, for example, the formation dynamics of hydrated electrons involve several intermediate transient species, which can be measured by femtosecond time-resolved IR spectroscopy [7].Solvation processes also play an important role in the context of electron transfer across interfaces between different materials. Such processes are of both fundamental interest and technological significance: The solvation dynamics in a quasi two-dimensional solvent at an interface is expected to differ from isotropic systems due to the reduced dimensionality and the resulting differences in solvent structure and motions [8]. In addition, the electronic coupling at polar molecule-metal interfaces opens a new decay channel for the excited-state population, leading to

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Novel Precursors of Solvated Electrons in Water: Evidence for a Charge Transfer Process

Cited by 172 publications

References 16 publications

Direct observation of the collapse of the delocalized excess electron in water

Direct observation of the collapse of the delocalized excess electron in water

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

Electron Dynamics at Polar Molecule–Metal Interfaces: Competition between Localization, Solvation, and Transfer

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