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Production and ionization energies of KnF (n = 2–6) clusters by thermal ionization mass spectrometry


S. R. Veličković, VINČA Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia.




The very small clusters of the type KnF are of particular importance since their first ionization energies (IEs) are lower than those of the alkali metal atoms. Theoretical calculation has demonstrated that this kind of cluster represents a potential 'building block' for cluster-assembly materials with unique structural, electronic, optical, magnetic, and thermodynamic properties. To date, however, there have been no experimental results on the IEs of KnF (n >2) clusters.


KnF (n = 2–6) clusters were produced by the evaporation of a solid potassium fluoride salt using a modified thermal ionization source of modified design, and mass selected by a magnetic sector mass spectrometer where their IEs were determined.


Clusters KnF (n = 3–6) were detected for the first time. The order of the ion intensities was K2F+> > K4F+> > K3F+K6F+ > K5F+. The determined IEs were 3.99 ± 0.20 eV for K2F, 4.16 ± 0.20 eV for K3F, 4.27 ± 0.20 eV for K4F, 4.22 ± 0.20 eV for K5F, and 4.31 ± 0.20 eV for K6F. The IEs of KnF increase slightly with the increase in potassium atom number from 2 to 6. We also observed that the presence of a fluorine atom leads to increasing ionization energy of bare metal potassium clusters.


The modified thermal ionization source provides an efficient way of obtaining the fluorine-doped potassium clusters. These results also present experimental proof that KnF (n = 2–6) clusters belong to the group of 'superalkali' species. Copyright © 2012 John Wiley & Sons, Ltd.