Structural Evolution of Small-Sized Phosphorus-Doped Boron Clusters: A Half-Sandwich-Structured PB₁₅ Cluster

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Boron clusters are known for their unique structural and electronic properties.
• Doping boron clusters with other elements, like phosphorus, can significantly alter their characteristics.
• Understanding the stability and structure of these doped clusters is crucial for potential applications.

Purpose of the Study:

• To theoretically investigate the structural evolution, electronic properties, and photoelectron spectra of phosphorus-doped boron clusters (PBn, n=3-17).
• To identify stable structural motifs and bonding characteristics within these doped clusters.
• To provide theoretical data for experimental identification of PBn clusters.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to determine lowest energy structures.
• Adaptive Natural Density Partitioning (AdNDP) and Electron Localization Function (ELF) analyses were used to investigate bonding.
• Photoelectron spectroscopy was simulated to predict characteristic spectral features.

Main Results:

• Most PBn- (n=3-17) clusters exhibit planar or quasi-planar structures, with exceptions like PB17-.
• PB7 adopts an umbrella-shaped structure, while PB15 displays a stable half-sandwich-like configuration with a large HOMO-LUMO gap (4.31 eV).
• Calculated photoelectron spectra provide distinct signatures for PBn- clusters, aiding in their identification.

Conclusions:

• The study elucidates the structural diversity and electronic properties of phosphorus-doped boron clusters.
• Specific stable structures and bonding patterns were identified for key clusters like PB7 and PB15.
• The theoretical findings support future experimental efforts in synthesizing and characterizing these doped boron clusters.