Theoretical and experimental investigation of geometry and stability of small potassium‐iodide KnI (n = 2–6) clusters

Small heterogeneous potassium‐iodide clusters are investigated by means of ab initio electronic structural methods together with experimental production and detection in mass spectrometry. Experiments were done by using Knudsen cell mass spectrometry (KCMS) modification method, which provided simultaneous generating of all KnI0,+1 (n = 2–6) clusters at once. Clusters with more than two potassium atoms are produced for the first time. The lowest lying isomers of those KnI0,+1 (n = 2–6) clusters were found by using a random‐kick procedure. The best description of growth of these clusters is the addition of one potassium atom to a smaller‐neighbor cluster. Subsequently, stability of these species was examined. In spite of general trend of decreasing of binding energies, the closed‐shell species have slightly larger stability with respect to the open‐shell species. Alternation of dissociation energies between closed‐shell and open‐shell clusters is presented. Experimental setup also allows determination of ionization energies of clusters: the obtained values are in the range of 3.46–3.98 eV, which classify these clusters as “superalkali.” For closed‐shell clusters, the theoretical adiabatic ionization energies are close to experimental values, whereas in the case of open‐shell clusters, the vertical ionization energies are those that are close to experimental values. Small “superalkali” heterogeneous potassium‐iodide clusters were characterized with Knudsen cell mass spectrometry. Species with more than two potassium atoms were produced for the first time. The low‐energy constitutional isomers of the neutral and positively charged clusters were determined using random‐kick procedure and density functional theory in combination with coupled cluster quantum chemistry methods. The study provides insights into clusters growth mechanism and isomers stability.