Mechanism and kinetics of hydrated electron diffusion.

  title={Mechanism and kinetics of hydrated electron diffusion.},
  author={Kafui A Tay and François-Xavier Coudert and Anne Boutin},
  journal={The Journal of chemical physics},
  volume={129 5},
Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be… 
14 Citations

Figures and Tables from this paper

Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons.

The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing, and the cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species.

Ab Initio Investigation of the Resonance Raman Spectrum of the Hydrated Electron.

All-electron ab initio calculations presented here demonstrate that both cavity and non-cavity models of e-(aq) afford significant red-shifts in the O-H stretching region, which is non-specific and arises due to electron penetration into frontier orbitals of the water molecules.

How Water-Ion Interactions Control the Formation of Hydrated Electron:Sodium Cation Contact Pairs.

It is shown that strengthening the ion-water interactions helps to maintain a favorable local solvation environment around Na+, which in turn forces water molecules in the first solvation shell of the cation to be unfavorably oriented toward the electron in a contact pair; stronger solvation of thecation also reduces the electronic overlap of eaq- with Na+.

Structure of the aqueous electron.

  • J. Herbert
  • Physics, Chemistry
    Physical chemistry chemical physics : PCCP
  • 2019
This Perspective reviews the known experimental properties of e-(aq) along with attempts to reproduce and understand them using both one-electron models and many-electrons quantum chemistry calculations, finding the overwhelming weight of the evidence continues to support the conventional excluded-volume picture of the aqueous electron.

Understanding the Photoexcitation of Room Temperature Ionic Liquids.

Photoexcitation of (neat) room temperature ionic liquids (RTILs) leads to the observation of transient species that are reminiscent of the composition of the RTILs themselves. In this minireview, we

Photoionization and electron radical recombination dynamics in photoactive yellow protein investigated by ultrafast spectroscopy in the visible and near-infrared spectral region.

It is suggested that solvated electrons could provide a new method to investigate the local dielectric environment inside PYP and thus help to understand the role of the protein in the photoisomerization process.

Shape-controlled synthesis and in situ characterisation of anisotropic Au nanomaterials using liquid cell transmission electron microscopy.

Understanding the mechanisms behind crystal nucleation and growth is a fundamental requirement for the design and production of bespoke nanomaterials with controlled sizes and morphologies. Herein,

Water entropy-driven electrochemical relaxation of dissolved oxygen in aerated refinery wastewater

AbstractThe results obtained in this paper show dissolved oxygen monolayer chemisorptions in gas bubbles in aerated and saturated refinery wastewater is water entropy-driven relaxation processes.

In vitro renal calculi destruction by a high-frequency glow discharge plasma

The method of stone fragmentation by high-frequency electrolyte plasma is concluded to be rather perspective and can be used in endoscopic urology for percutaneous and transurethral lithotripsy.



Molecular simulation of a hydrated electron at different thermodynamic state points

The properties of the hydrated electron are studied by quantum-classical molecular-dynamics simulation in a wide range of temperature and pressure, from ambient to supercritical conditions. The

Molecular dynamics simulations of electron-alkali cation pairs in bulk water.

The overall trend of the UV-vis hydrated absorption spectra, namely, the shift toward shorter wavelengths at high ionic strengths, is fairly well reproduced, which confirms the hypothesis of statistical distribution of the cations and solvated electrons.

Behavior of the hydrated electron at different temperatures: structure and absorption spectrum

The properties of a solvated electron have been investigated at 300 and 373 K by use of path integral Monte Carlo methods with a refined pseudopotential, both with and without many-body polarization

Quantum simulation study of the hydrated electron

An excess electron in a sample of classical water molecules at room temperature has been simulated using path integral techniques. The electron–water interaction is modeled by a pseudopotential with

Molecular dynamics simulation of an excess charge in water using mobile Gaussian orbitals

For mixed quantum‐classical molecular dynamics simulations of solvated excess charges a novel and efficient method to expand the solute electronic wave function in a distributed Gaussian basis with a

Detailed Investigation of the Femtosecond Pump−Probe Spectroscopy of the Hydrated Electron

We recently reported the first pump−probe measurements on the hydrated electron with sufficient time resolution (∼35 fs) to directly observe the initial processes in the solvation dynamics of this

Dynamics of excess electron migration, solvation, and spectra in polar molecular clusters

The dynamics of excess electron localization, migration, and solvation in water and ammonia clusters, and the time‐resolved spectroscopic consequences of these processes, are investigated via

Excess electron in water at different thermodynamic conditions.

  • M. Boero
  • Chemistry, Physics
    The journal of physical chemistry. A
  • 2007
A hydrated electron in water at different densities and temperatures is studied via a set of density functional based molecular dynamics simulations, showing that a localization of an excess electron

Diffusive transport of the hydrated electron : a pseudoclassical model

A pseudoclassical model that is used to simulate the adiabatic dynamical response of the electron is applied to halide-like ions in water for different solute-solvent potentials in order to evaluate

Molecular dynamics study of an aqueous SrCl2 solution

A molecular dynamics simulation of a 1.1 m SrCl/sub 2/ solution was performed with an improved central force model for water at the experimental density at room temperature. The ion-water and ion-ion