MB₃₈(M=Be and Zn): A Quasi-Planar Structure Rather Than a Core-Shell Octahedral Borospherene Structure

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Previous studies identified core-shell octahedral structures as global minima for Be@B38 and Zn@B38 clusters.
• The stability and structural characteristics of metal-doped boron clusters are crucial for understanding their properties.

Purpose of the Study:

• To investigate lower energy structures for MB38 (M=Be, Zn) clusters.
• To challenge the previously reported global minima configurations.
• To elucidate the bonding and electronic properties of these novel structures.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to determine cluster structures and energies.
• Natural atomic charges, valence electron density, and electron localization function (ELF) analyses were performed.
• Simulations of photoelectron spectra for anionic structures were conducted.

Main Results:

• Quasi-planar configurations of MB38 (M=Be, Zn) were found to have lower energies than core-shell octahedral structures.
• Beryllium atoms reside on the convex surface, while zinc atoms attach to the top three boron atoms of the quasi-planar B38 isomer.
• Analyses indicate charge transfer complex formation (Be2+B382- and Zn1+B381-) driven by electrostatic interactions.

Conclusions:

• The quasi-planar structures represent more stable configurations for Be@B38 and Zn@B38 clusters.
• The bonding is primarily governed by electrostatic interactions between the doped metal atom and the B38 framework.
• Simulated photoelectron spectra provide a basis for experimental validation and structural identification.