Hydrogen Forms in Water by Proton Transfer to a Distorted Electron

Solvated electrons are ubiquitous intermediates in radiation-induced processes, with their lifetime being determined by quenching processes, such as the direct reaction with protons under acidic conditions. Ab initio molecular dynamics simulations allow us to unravel with molecular resolution the ul...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry. B 2010-01, Vol.114 (2), p.915-920
Main Authors: Marsalek, Ondrej, Frigato, Tomaso, VandeVondele, Joost, Bradforth, Stephen E, Schmidt, Burkhard, Schütte, Christof, Jungwirth, Pavel
Format: Article
Language:English
Subjects:
B: Statistical Mechanics, Thermodynamics, Medium Effects
Computer Simulation
Electrons
Hydrogen - chemistry
Molecular Dynamics Simulation
Protons
Water - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Solvated electrons are ubiquitous intermediates in radiation-induced processes, with their lifetime being determined by quenching processes, such as the direct reaction with protons under acidic conditions. Ab initio molecular dynamics simulations allow us to unravel with molecular resolution the ultrafast reaction mechanism by which the electron and proton react in water. The path to a successful reaction involves a distortion and contraction of the hydrated electron and a rapid proton motion along a chain of hydrogen bonds, terminating on the water molecule most protruding into the electron cloud. This fundamental reaction is thus decidedly shown to be of a proton-transfer rather than electron-transfer character. Due to the desolvation penalty connected with breaking of the hydration shells of these charged particles, the reaction is, however, not diffusion-limited, in agreement with the interpretation of kinetics measurements.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp908986z