Femtosecond spectroscopy of an encounter pair radical (H3O+.cntdot..cntdot..cntdot.e-)hyd in concentrated aqueous solution

Gauduel, Y.; Pommeret, S.; Migus, A.; Yamada, N.; Antonetti, A.

doi:10.1021/ja00164a013

Cited by 52 publications

(42 citation statements)

References 2 publications

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“…Therefore the recombination is sufficiently fast to obscure the expected isosbestic behavior. We have found that broader, less intense pulses are typically produced with a 1 mm KDP crystal, as was used by Gaudel et al [ 19,41,43]. We believe this is the source of the discrepancy between our results (high intensity ) and that of Gaudel et al (low intensity).…”

Section: Resultscontrasting

confidence: 59%

“…The ultraviolet photons comprising the femtosecond excitation pulse are at 4 eV, thus three photons are required to exceed the photoionization threshold of liquid water. The electron will therefore have at most 3.5 eV of excess energy, which is likely to result in a thermalization distance that greatly exceeds the Onsager distance of about 7 A [ 38,39, 41,48]. The Onsager distance is the distance at which the Coulomb electron-cation interaction energy is equal to the thermal energy kT.…”

Section: Possible Model For Intensity-dependent Kinetics Let Us Now Cmentioning

confidence: 99%

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Intensity dependent geminate recombination in water

Long

Shi

et al. 1991

Chemical Physics Letters

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We have observed an intensity dependent geminate recombination of electrons in neat water. Since the recombination dynamics occurs on a time scale comparable to the salvation dynamics, the kinetics characteristic of an isosbestic wavelength are obscured. We have hypothesized that this intensity-dependent geminate recombination is due to the existence of two mechanisms for electron production with different characteristic thermalization distances. These results clarify the discrepancy between cxperiments at higher intensities and those at lower intensities

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Section: Resultscontrasting

confidence: 59%

Section: Possible Model For Intensity-dependent Kinetics Let Us Now Cmentioning

confidence: 99%

Intensity dependent geminate recombination in water

Long

Shi

et al. 1991

Chemical Physics Letters

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“…The pump-and-probe technique made it possible to obtain reasonably good resolution transient spectra even in the fastest solvent, water. [15][16][17][18][19][20][21] The theoretical methods and approaches of the nonadiabatic chemical processes have experienced a similarly rapid development. Nonadiabatic molecular dynamics techniques treating the solute quantum mechanically, while describing the bath classically, are now widely employed for nonadiabatic con-densed phase processes.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic molecular dynamics simulation of photoexcitation experiments for the solvated electron in methanol

Mináry

Túri

Rossky

1999

The Journal of Chemical Physics

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Articles you may be interested inMoving solvated electrons with light: Nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF) Nonadiabatic quantum molecular dynamics simulations have been performed to simulate the pump-and-probe photoexcitation experiments of the ground state equilibrium solvated electron in methanol carried out by Barbara et al. ͓Chem. Phys. Lett. 232, 135 ͑1995͔͒. We have characterized both the time evolution of the quantum solute, the solvated electron, and the solvation response of the classical methanol bath. The quantum energy gap provides an excellent tool to gain insight into the underlying microscopic details of the solvation process. The solvent response is characterized for both processes by a fast Gaussian component and a biexponential decay. The present results suggest that the residence time of the solvated electron in the first excited state is substantially longer than inferred from the cited experiments. The experimentally observed fast exponential portion of the relaxation more likely corresponds to the adiabatic solvent response than to the lifetime of the excited state electron. By comparing to photoexcitation simulations in water, it is shown that the simulated excited state lifetime is about three times longer in methanol than in water, predicting a less substantial increase than a recent calculation based on nonadiabatic coupling elements alone. Hydrogen-bonding statistical analysis provides interesting additional details about the dynamics. We find that the hydrogen-bonding network is significantly different in the first solvent shell around the electron in ground and first excited states, the distribution around the latter, larger and more diffuse, ion resembling more that of the pure liquid. Transformation of the corresponding hydrogen bonding structures takes place on a 1 ps time scale.

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“…The problem of the solvated electron or equilibrated electron in water has been of great experimental [1][2][3][4][5][6][7][8] and theoretical interest. [9][10][11][12][13][14][15][16][17][18] Although the absorption spectra of the solvated electron in water are understood, 10,14 it is only recently that the details of the dynamics of electron solvation have begun to emerge from ultrafast absorption spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Femtosecond Electron Solvation Kinetics in Water

Shi

Long

et al. 1996

J. Phys. Chem.

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Recent experimental and theoretical studies of electron solvation in liquid water have led to a detailed kinetic picture of this process. The electron solvation dynamics can be viewed as an excited state relaxation process between different electronic energy levels of the solvated electron. Simulations have suggested the importance of direct relaxation from upper excited electronic states as well as from the lowest excited electronic state (the wet electron state) to the ground electronic state. Using this as a model to analyze the experimental data, it is found that the quantum yield of wet electron formation cannot be less than 0.5 and that the peak of the wet electron absorption spectrum shifts to the IR with a decrease of wet electron formation quantum yield, with limiting values for the peak of 1.1-1.5 eV.

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Femtosecond spectroscopy of an encounter pair radical (H3O+.cntdot..cntdot..cntdot.e-)hyd in concentrated aqueous solution

Cited by 52 publications

References 2 publications

Intensity dependent geminate recombination in water

Intensity dependent geminate recombination in water

Nonadiabatic molecular dynamics simulation of photoexcitation experiments for the solvated electron in methanol

Femtosecond Electron Solvation Kinetics in Water

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