E3M3+ (E=C–Pb, M=Li–Cs) Clusters: The Smallest Molecular Stars. Issue 47 (28th July 2017)

• Record Type: Journal Article
• Authors: Contreras, Maryel; Pan, Sudip; Orozco‐Ic, Mesías; Cabellos, José Luis; Merino, Gabriel
• Is Part Of: Chemistry. Volume 23:Issue 47(2017)
• Page Start: 11430
• Page End: 11436
• Publication Date: 2017-07-28
• Subjects: cluster compounds -- density functional calculations -- minimum search algorithms -- tetracoordinate atoms -- superalkali; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201702413
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Extensive potential energy surface explorations of twenty‐five clusters with the formula E3 M3 + (E=Group 14 element and M=Group 1 element) through density functional theory and high‐level ab initio computations reveal that the lowest‐energy isomer for all these systems corresponds to a non‐classical D 3 h star‐like structure in the singlet state, where three M atoms interact electrostatically with the triangular E3 core, occupying three bridging positions around it. More than 18 200 calculations were done in the search for the minima structures, starting with a first phase at the PBE0/LANL2DZ level and ending with an analysis of the most representative clusters at the CCSD(T)/def2‐TZVP//PBE0/def2‐TZVP level. The title clusters represent the smallest molecular stars with three planar tetracoordinate E atoms (E=Group 14 element). All these E3 M3 + clusters behave like superalkali cations with small vertical electron affinities (smaller than Cs), large vertical electron detachment energies, and HOMO–LUMO energy gaps. Their energetics, bonding, and electron delocalization are discussed in detail. The high stability of these clusters is reflected from the large dissociation energy needed for different dissociation channels. The electron delocalization is confirmed by the presence of two delocalized π electrons over the E3 core and strong diatropic responses. Abstract : A star is born : Twenty‐five small clusters with a minimum energy D 3 h structure were obtained through a robust and extensive potential energy surface exploration. Each E3 M3 + (E=C–Pb, M=Li–Cs, see figure) molecular star has three planar tetracoordinate E atoms and three bridging M atoms, and shows a diatropic response and superalkali behavior.