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Holding onto Electrons in Alkali Metal Halide Clusters: Decreasing Polarizability with Increasing Coordination

Zhang, Chaofan; Andersson, Tomas; Svensson, Svante; Bjorneholm, Olle; Huttula, Marko; Mikkela, Mikko-Heikki; Anin, Dmitri; Tchaplyguine, Maxim LU and Öhrwall, Gunnar LU (2012) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 116(49). p.12104-12111
Abstract
The connection between the electronic polarizability and the decrease of the system size from macroscopic solid to nanoscale clusters has been addressed in a combined experimental and model-calculation study. A beam of free neutral potassium chloride clusters has been probed using synchrotron-radiation-based photoelectron spectroscopy. The introduction of "effective" polarizability for chlorine, lower than that in molecules and dimers and decreasing with increasing coordination, has allowed us to significantly improve the agreement between the experimental electron binding energies and the electrostatic model predictions. Using the calculated site-specific binding energies, we have been able to assign the spectral details of the cluster... (More)
The connection between the electronic polarizability and the decrease of the system size from macroscopic solid to nanoscale clusters has been addressed in a combined experimental and model-calculation study. A beam of free neutral potassium chloride clusters has been probed using synchrotron-radiation-based photoelectron spectroscopy. The introduction of "effective" polarizability for chlorine, lower than that in molecules and dimers and decreasing with increasing coordination, has allowed us to significantly improve the agreement between the experimental electron binding energies and the electrostatic model predictions. Using the calculated site-specific binding energies, we have been able to assign the spectral details of the cluster response to the ionizing X-ray radiation, and to explain its change with cluster size. From our assignments we find that the higher-coordination face-atom responses in the K 3p spectra increase significantly with increasing cluster size relative to that of the edge atoms. The reasons behind the decrease of polarizability predicted earlier by ab initio calculations are discussed in terms of the limited mobility of the electron clouds caused by the interaction with the neighboring ions. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
116
issue
49
pages
12104 - 12111
publisher
The American Chemical Society
external identifiers
  • wos:000312175900014
  • scopus:84871010476
ISSN
1520-5215
DOI
10.1021/jp307786z
language
English
LU publication?
yes
id
e9d8e801-45e1-40c3-a249-fea7d813b901 (old id 3366641)
date added to LUP
2013-02-01 08:46:55
date last changed
2017-09-10 04:17:52
@article{e9d8e801-45e1-40c3-a249-fea7d813b901,
  abstract     = {The connection between the electronic polarizability and the decrease of the system size from macroscopic solid to nanoscale clusters has been addressed in a combined experimental and model-calculation study. A beam of free neutral potassium chloride clusters has been probed using synchrotron-radiation-based photoelectron spectroscopy. The introduction of "effective" polarizability for chlorine, lower than that in molecules and dimers and decreasing with increasing coordination, has allowed us to significantly improve the agreement between the experimental electron binding energies and the electrostatic model predictions. Using the calculated site-specific binding energies, we have been able to assign the spectral details of the cluster response to the ionizing X-ray radiation, and to explain its change with cluster size. From our assignments we find that the higher-coordination face-atom responses in the K 3p spectra increase significantly with increasing cluster size relative to that of the edge atoms. The reasons behind the decrease of polarizability predicted earlier by ab initio calculations are discussed in terms of the limited mobility of the electron clouds caused by the interaction with the neighboring ions.},
  author       = {Zhang, Chaofan and Andersson, Tomas and Svensson, Svante and Bjorneholm, Olle and Huttula, Marko and Mikkela, Mikko-Heikki and Anin, Dmitri and Tchaplyguine, Maxim and Öhrwall, Gunnar},
  issn         = {1520-5215},
  language     = {eng},
  number       = {49},
  pages        = {12104--12111},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Holding onto Electrons in Alkali Metal Halide Clusters: Decreasing Polarizability with Increasing Coordination},
  url          = {http://dx.doi.org/10.1021/jp307786z},
  volume       = {116},
  year         = {2012},
}