VINČA Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001, Belgrade, Serbia.
Rapid Commun Mass Spectrom. 2012 Aug 30;26(16):1761-6. doi: 10.1002/rcm.6284.
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.
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.
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.
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.
K(n)F(n=2-6)这种非常小的团簇尤为重要,因为其第一电离能(IE)低于碱金属原子。理论计算表明,这种团簇代表了一种具有独特结构、电子、光学、磁性和热力学性质的团簇组装材料的潜在“构建块”。然而,迄今为止,尚无关于 K(n)F(n>2)团簇的 IE 的实验结果。
使用改良的热电离源,通过蒸发固态氟化钾盐来产生 K(n)F(n=2-6)团簇,并用磁扇形质量分析仪对其进行质量选择,以确定其 IE。
首次检测到 K(n)F(n=3-6)团簇。离子强度的顺序为 K(2)F(+)>>K(4)F(+)>>K(3)F(+)>K(6)F(+)>K(5)F(+)。测定的 IE 为 K(2)F 为 3.99±0.20eV,K(3)F 为 4.16±0.20eV,K(4)F 为 4.27±0.20eV,K(5)F 为 4.22±0.20eV,K(6)F 为 4.31±0.20eV。随着钾原子数从 2 增加到 6,K(n)F 的 IE 略有增加。我们还观察到,一个氟原子的存在导致裸露金属钾团簇的电离能增加。
改良的热电离源为获得氟掺杂钾团簇提供了一种有效的方法。这些结果也提供了实验证据,证明 K(n)F(n=2-6)团簇属于“超碱金属”物种。