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


Savolainen, Janne; Uhlig, Frank; Ahmed, Saima; Hamm, Peter; Jungwirth, Pavel (2014). Direct observation of the collapse of the delocalized excess electron in water. Nature Chemistry, 6(8):697-701.

Abstract

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.

Abstract

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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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:August 2014
Deposited On:09 Oct 2014 09:00
Last Modified:18 Apr 2018 11:45
Publisher:Nature Publishing Group
ISSN:1755-4330
Funders:Swiss National Science Foundation (SNF) through the NCCR MUST, Czech Science Foundation, Academy of Sciences for the Praemium Academie award, John von Neumann Institute for Computing (NIC)
OA Status:Green
Publisher DOI:https://doi.org/10.1038/nchem.1995
PubMed ID:25054939
Project Information:
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation (SNF) through the NCCR MUST
  • : Funder
  • : Grant ID
  • : Project TitleCzech Science Foundation
  • : Funder
  • : Grant ID
  • : Project TitleAcademy of Sciences for the Praemium Academie award
  • : Funder
  • : Grant ID
  • : Project TitleJohn von Neumann Institute for Computing (NIC)

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