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Charge delocalization dynamics of ammonia in different hydrogen bonding environments: free clusters and in liquid water solution

Lindblad, A.; Bergersen, H.; Pokapanich, W.; Tchaplyguine, Maxim LU ; Ohrwall, G. and Bjorneholm, O. (2009) In Physical Chemistry Chemical Physics 11(11). p.1758-1764
Abstract
Valence and core level photoelectron spectra and Auger electron spectra of ammonia in pure clusters have been measured. The Auger electron spectra of gas-phase ammonia, pure ammonia clusters and ammonia in aqueous solution are compared and interpreted via ab initio calculations of the Auger spectrum of the ammonia monomer and dimer. The calculations reveal that the final two-hole valence states can be delocalized over both ammonia molecules. Features at energies pertaining to delocalized states involving one, or more, hydrogen bonding orbitals can be found in both the ammonia cluster Auger electron spectrum and in that of the liquid solvated molecule. The lower Coulombic repulsion between two delocalized valence final state holes gives... (More)
Valence and core level photoelectron spectra and Auger electron spectra of ammonia in pure clusters have been measured. The Auger electron spectra of gas-phase ammonia, pure ammonia clusters and ammonia in aqueous solution are compared and interpreted via ab initio calculations of the Auger spectrum of the ammonia monomer and dimer. The calculations reveal that the final two-hole valence states can be delocalized over both ammonia molecules. Features at energies pertaining to delocalized states involving one, or more, hydrogen bonding orbitals can be found in both the ammonia cluster Auger electron spectrum and in that of the liquid solvated molecule. The lower Coulombic repulsion between two delocalized valence final state holes gives higher kinetic energy of the Auger electrons which is also observed in the spectra. This decay path-specific to the condensed phase-is responsible for more than 5% of the total cluster Auger intensity. Moreover, this interpretation is also applicable to the solid phase since the same features have been observed, but not assigned, in the Auger spectrum of solid ammonia. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
11
issue
11
pages
1758 - 1764
publisher
Royal Society of Chemistry
external identifiers
  • wos:000263838200012
  • scopus:61649127608
ISSN
1463-9084
DOI
10.1039/b815657c
language
English
LU publication?
yes
id
dc827b4c-8e67-4234-b6f3-388c0b41e4ce (old id 1370938)
date added to LUP
2009-05-08 12:27:42
date last changed
2017-10-01 04:14:42
@article{dc827b4c-8e67-4234-b6f3-388c0b41e4ce,
  abstract     = {Valence and core level photoelectron spectra and Auger electron spectra of ammonia in pure clusters have been measured. The Auger electron spectra of gas-phase ammonia, pure ammonia clusters and ammonia in aqueous solution are compared and interpreted via ab initio calculations of the Auger spectrum of the ammonia monomer and dimer. The calculations reveal that the final two-hole valence states can be delocalized over both ammonia molecules. Features at energies pertaining to delocalized states involving one, or more, hydrogen bonding orbitals can be found in both the ammonia cluster Auger electron spectrum and in that of the liquid solvated molecule. The lower Coulombic repulsion between two delocalized valence final state holes gives higher kinetic energy of the Auger electrons which is also observed in the spectra. This decay path-specific to the condensed phase-is responsible for more than 5% of the total cluster Auger intensity. Moreover, this interpretation is also applicable to the solid phase since the same features have been observed, but not assigned, in the Auger spectrum of solid ammonia.},
  author       = {Lindblad, A. and Bergersen, H. and Pokapanich, W. and Tchaplyguine, Maxim and Ohrwall, G. and Bjorneholm, O.},
  issn         = {1463-9084},
  language     = {eng},
  number       = {11},
  pages        = {1758--1764},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Charge delocalization dynamics of ammonia in different hydrogen bonding environments: free clusters and in liquid water solution},
  url          = {http://dx.doi.org/10.1039/b815657c},
  volume       = {11},
  year         = {2009},
}