Structural Evolution and Electronic Properties of Two Sulfur Atom-Doped Boron Clusters

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Boron clusters are electron-deficient and typically do not form linear chains.
• The structural and electronic properties of doped boron clusters are crucial for understanding their potential applications.

Purpose of the Study:

• To theoretically investigate the structural evolution, electronic properties, and photoelectron spectra of sulfur-doped boron clusters (S₂Bₙ⁰/⁻, n = 2-13).
• To analyze the impact of sulfur doping on the stability, aromaticity, and structural characteristics of boron clusters.

Main Methods:

• Theoretical calculations of structural evolution, electronic properties, and photoelectron spectra.
• Analysis using Atoms in Molecules (AIM) and electron localization function (ELF) methods.
• Bonding analysis using the Natural Population Analysis (NPA) and Natural Resonance Theory (NRT) methods.

Main Results:

• Sulfur doping induces a structural transition from linear to planar/quasi-planar configurations in S₂Bₙ⁰/⁻ clusters.
• S₂B₂⁰/⁻ clusters exhibit the largest HOMO-LUMO gap and S₂B₂⁻ shows superior relative stability.
• Various degrees of π and σ aromaticity/antiaromaticity were identified in different doped clusters, with some achieving double aromaticity.

Conclusions:

• Sulfur doping significantly modifies boron cluster structures, enhancing stability and introducing novel electronic and aromatic properties.
• The calculated photoelectron spectra provide a basis for experimental identification of these doped boron clusters.
• This research expands the database of doped boron cluster structures and offers insights for designing new nanomaterials and nanodevices.