Formation and ionization energies of small chlorine‐doped lithium clusters by thermal ionization mass spectrometry

Abstract

Theoretical calculations have shown that the first ionization energy of clusters of the type Li(n) Cl (n ≥2), with more than eight valent electrons, is lower than that of alkali metal atoms; hence they are named superalkali. Superalkali clusters can mimic the chemical behavior of alkali metals and may be used as building blocks of new cluster-assembled materials. There is currently no reliable experimental proof of this kind of clusters and such proof is required. The Li(n) Cl (n = 2-6) clusters were produced by a thermal ionization source of modified design, and mass selected by a magnetic-sector mass spectrometer. The modification pertains to the replacement of the side filaments by a cylinder in the triple-filament thermal ionization source. The sample, which is LiCl salt, was pressed into a ring and placed on the inner wall of the cylinder. It was observed that the ions of clusters with an even number of lithium atoms (Li(2) Cl(+) , Li(4) Cl(+) , Li(6) Cl(+) ) are more stable than the odd-numbered ones (Li(5) Cl(+) , Li(3) Cl(+) ). The ionization energies were determined to be 3.98 ± 0.25 eV for Li(2) Cl, 4.10 ± 0.25 eV for Li(3) Cl, 3.90 ± 0.25 eV for Li(4) Cl, 4.01 ± 0.25 eV for Li(5) Cl, and 4.09 ± 0.25 eV for Li(6) Cl. The presence of a halogen atom reduces the ionization energy of the metal clusters. The thermal ionization source of modified design presents a suitable simple way to obtaining and measuring the ionization energies of very small lithium monochloride clusters. Clusters Li(n) Cl, n = 4 to 6, were detected for the first time.