Modulation of Electronic and Optical Properties in Li‐Doped Boron Clusters Under Dual Regulation Strategy

ABSTRACT

In this work, two distinct regulation strategies—atomic doping modification and oriented external electric field (OEEF) modulation—are adopted to achieve systematic and continuous tuning of the electronic and optical properties of lithium‐doped boron clusters. First, using the Crystal Structure Analysis by Particle Swarm Optimization (CALYPSO) structural prediction algorithm combined with density functional theory (DFT), the geometric structures, electronic properties, and optical properties are systematically investigated for Li‐doped B ₈ ⁻ clusters. Structural searches reveal that the introduction of Li atoms can completely reconstruct the planar B ₈ ⁻ framework into a three‐dimensional structure with the Li atom located at the periphery of the boron ring. Based on the global minimum structures, we calculate the average binding energy, dissociation energy, second‐order energy difference, and HOMO–LUMO gap. Calculated results indicate that the umbrella‐shaped LiB ₈ ⁻ cluster with C _7v point group symmetry exhibits relatively high stability. Subsequently, charge transfer behavior is analyzed, and the photoelectron, infrared, and Raman spectra are simulated using the Multiwfn program. Second, with the global minimum structure of LiB ₈ ⁻ cluster as the research prototype, OEEFs with different directions and intensities are applied to systematically explore the variations in structural parameters, dipole moment, energy levels, charge distribution, as well as IR and Raman spectra, without altering the original geometric configuration. Results demonstrate that OEEFs enable effective and continuous regulation of multiple electronic and optical properties. This work provides new insights into dual mode property tuning and offers theoretical guidance for the design of boron‐based functional nanomaterials.