Y@Cu₁₅: a novel spherical aromatic 18-ce bare superatomic molecular cluster

Area of Science:

• * Computational chemistry and materials science.
• * Investigating novel molecular clusters and their properties.

Background:

• * Understanding molecular clusters is key to discovering new materials with unique stability and electronic features.
• * Prototypical species are sought to expand knowledge of well-defined, stable structures.

Purpose of the Study:

• * To investigate the structural and electronic properties of the Yttrium@Copper15 (Y@Cu15) binary cluster.
• * To determine the stability and bonding characteristics of encapsulated yttrium within a copper cage.
• * To explore the potential catalytic applications of the Y@Cu15 cluster.

Main Methods:

• * Employed a modified basin-hopping (MBH) structure search method.
• * Utilized computational analysis for interaction energy, charge transfer, and electronic structure.
• * Performed through-space nuclear independent chemical shift (NICS) and electron density of delocalized bond (EDDB_G) analyses.

Main Results:

• * Identified a stable Y@Cu15 cluster with a low-symmetry C2v geometry, featuring an encapsulated yttrium atom.
• * Calculated a significant interaction energy of -220.4 kcal mol-1, driven by electrostatic and orbital contributions, including Y→Cu15 charge transfer.
• * Confirmed the cluster follows the 1S21P61D10 superatomic shell model, exhibiting spherical aromaticity via NICS and EDDB_G analyses.
• * Observed electron-deficient copper sites suggesting catalytic potential.

Conclusions:

• * Y@Cu15 represents a novel, medium-sized spherical aromatic superatomic cluster.
• * The cluster possesses promising reactive sites for catalysis.
• * Findings expand the understanding of superatomic cluster chemistry and encourage further research into reactivity and applications.