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research article

Time-dependent density functional theory molecular dynamics simulations of liquid water radiolysis

Tavernelli, Ivano
•
Gaigeot, Marie-Pierre
•
Vuilleumier, Rodolphe
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2008
ChemPhysChem

The early stages of the Coulomb explosion of a doubly ionized water molecule immersed in liquid water are investigated with time-dependent density functional theory molecular dynamics (TD-DFT MD) simulations. Our aim is to verify that the double ionization of one target water molecule leads to the formation of atomic oxygen as a direct consequence of the Coulomb explosion of the molecule. To that end, we used TD-DFT MD simulations in which effective molecular orbitals are propagated in time. These molecular orbitals are constructed as a unitary transformation of maximally localized Wannier orbitals, and the ionization process was obtained by removing two electrons from the molecular or-bitals with symmetry 1B(1), 3A(1), 1B(2), and 2A(1) in turn. We show that the doubly charged H2O2+ molecule explodes into its three atomic fragments in less than 4 fs, which leads to the formation of one isolated oxygen atom whatever the ionized molecular orbital. This process is followed by the ultrafast transfer of an electron to the ionized molecule in the first femtosecond. A foster dissociation pattern can be observed when the electrons are removed from the molecular orbitals of the innermost shell. A Bader analysis of the charges carried by the molecules during the dissociation trajectories is also reported.

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Type
research article
DOI
10.1002/cphc.200800177
Web of Science ID

WOS:000260036000019

Author(s)
Tavernelli, Ivano
Gaigeot, Marie-Pierre
Vuilleumier, Rodolphe
Stia, Carlos
du Penhoat, Marie-Anne Herve
Politis, Marie-Francoise
Date Issued

2008

Published in
ChemPhysChem
Volume

9

Start page

2099

End page

2103

Subjects

density functional calculations

•

ionization in liquids

•

molecular dynamics

•

radiolysis

•

water chemistry

•

Localized Wannier Functions

•

Electron-Density

•

Heavy-Ions

•

Pseudopotentials

•

Ionization

•

States

•

Model

•

Dna

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
SB  
Available on Infoscience
November 30, 2010
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/60985
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