RESUMEN
The theoretical calculations have predicted that nonmetal-doped potassium clusters can be used in the synthesis of a new class of charge-transfer salts which can be considered as potential building blocks for the assembly of novel nanostructured material. In this work, K(n)Cl (n = 2-6) and K(n)Cl(n-1) (n = 3 and 4) clusters were produced by vaporization of a solid potassium chloride salt in a thermal ionization mass spectrometry. The ionization energies (IEs) were measured, and found to be 3.64 ± 0.20 eV for K(2)Cl, 3.67 ± 0.20 eV for K(3)Cl, 3.62 ± 0.20 eV for K(4)Cl, 3.57 ± 0.20 eV for K(5)Cl, 3.69 ± 0.20 eV for K(6)Cl, 3.71 ± 0.20 eV for K(3)Cl(2) and 3.72 ± 0.20 eV for K(4)Cl(3). The K(n)Cl(+) (n = 3-6) clusters were detected for the first time in a cluster beam generated by the thermal ionization source of modified design. Also, this work is the first to report experimentally obtained values of IEs for K(n)Cl(+) (n = 3-6) and K(n)Cl(n-1) (+) (n = 3 and 4) clusters. The ionization energies for K(n)Cl(+) and K(n)Cl(n-1) (+) clusters are much lower than the 4.34 eV of the potassium atom; hence, these clusters should be classified as 'superalkali' species.
RESUMEN
RATIONALE: The very small clusters of the type K(n)F 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 K(n)F (n >2) clusters. METHOD: K(n)F (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. RESULTS: Clusters K(n)F (n = 3-6) were detected for the first time. The order of the ion intensities was K(2)F(+)> > K(4)F(+)> > K(3)F(+)K(6)F(+)> K(5)F(+). The determined IEs were 3.99 ± 0.20 eV for K(2)F, 4.16 ± 0.20 eV for K(3)F, 4.27 ± 0.20 eV for K(4)F, 4.22 ± 0.20 eV for K(5)F, and 4.31 ± 0.20 eV for K(6)F. The IEs of K(n)F 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. CONCLUSIONS: The modified thermal ionization source provides an efficient way of obtaining the fluorine-doped potassium clusters. These results also present experimental proof that K(n)F (n = 2-6) clusters belong to the group of 'superalkali' species.
RESUMEN
The electronic structure and properties of dipotassiummonohalides are important for understanding the unique physical and chemical behavior of M(n)X systems. In the present study, K(2) X (here X=F, Cl, Br, I) clusters were generated in the vapor over salts of the corresponding potassium halide, using a magnetic sector thermal ionization mass spectrometer. The ionization energies obtained for K(2)F, K(2)Cl, K(2)Br, and K(2)I molecules were 3.82 ± 0.1 eV, 3.68 ± 0.1 eV, 3.95 ± 0.1 eV, and 3.92 ± 0.1, respectively. These experimental values of ionization energies for K(2) X (X=F, Br, and I) are presented for the first time. The ionization energy of K(2)Cl determined by thermal ionization corresponds to previous results obtained by photoionization mass spectrometry, and it agrees with the theoretical ionization energy calculated by the ab initio method. The presently obtained results support previous theoretical predictions that the excess electron in dipotassiummonohalide clusters is delocalized over two potassium atoms, which is characteristic for F-center clusters.