Na2Aln−/0 （n = 2-15）簇的结构和电子性质：理论研究

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics Pub Date : 2025-09-30 DOI:10.1016/j.chemphys.2025.112957

Kai Wang, Hanyu Du, Rui Chen, Chaoyong Wang

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引用次数: 0

摘要

本文采用全局优化和密度泛函理论计算的方法研究了Na2Aln−/0 （n = 2-15）簇的结构演化和电子性质。阴离子Na2Aln−(n = 2-15)簇的结构通过模拟光电子能谱与实验对应物的匹配来确定。结构分析表明，除了小尺寸（n≤4）阴离子外，Na原子完全吸附在Aln骨架表面并充当电子供体。大多数Na2Aln簇通常采用两个Na原子吸附在原始基态Aln结构上的最佳配置。平均结合能趋势表明在较大的团簇中稳定性增强。中性Na2Al6簇表现出超原子行为，具有较大的HOMO-LUMO间隙和显著的二阶能差。其电子构型（1S）2(1P)6(1D)10(2S)2满足典型分子轨道分析所揭示的20电子闭壳规则，证实了其稳定性。

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Structures and electronic properties of Na2Aln−/0 (n = 2–15) clusters: A theoretical investigation

Herein, we investigate the structural evolution and electronic properties of Na₂Al_n^−/0 (n = 2–15) clusters by employing global optimization and density functional theory calculations. The structures of anionic Na₂Al_n⁻ (n = 2–15) clusters were determined by matching the simulated photoelectron spectra with their experimental counterparts. Structural analysis reveals that Na atoms adsorb exclusively on the surface of the Al_n framework and act as electron donors, except in small-sized (n ≤ 4) anionic species. Most Na₂Al_n clusters typically adopt an optimal configuration in which two Na atoms are adsorbed on the pristine ground-state Al_n structure. The average binding energy trend reveals enhanced stability in larger clusters. The neutral Na₂Al₆ cluster exhibits superatomic behavior, characterized by a large HOMO-LUMO gap and a significant second-order energy difference. This stability is confirmed by its electron configuration, (1S)²(1P)⁶(1D)¹⁰(2S)², which satisfies the 20-electron rule for a closed shell as revealed by canonical molecular orbital analysis.

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来源期刊

Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

4.60

自引率

4.30%

发文量

278

审稿时长

39 days

期刊介绍： Chemical Physics publishes experimental and theoretical papers on all aspects of chemical physics. In this journal, experiments are related to theory, and in turn theoretical papers are related to present or future experiments. Subjects covered include: spectroscopy and molecular structure, interacting systems, relaxation phenomena, biological systems, materials, fundamental problems in molecular reactivity, molecular quantum theory and statistical mechanics. Computational chemistry studies of routine character are not appropriate for this journal.