摘要
使用密度泛函理论并结合粒子群优化算法对小尺寸Zr_(n)Al(n=2~12)团簇的结构进行了系统的筛选,成功确定了其最低能量结构。研究结果表明,随着团簇中锆(Zr)原子数的递增,团簇的几何形态逐步向三维结构演化,同时在n=9时,整个结构开始趋于笼状结构,其中Zr_(12)Al的最低能量结构为Ih对称性的二十面体结构。稳定性评估指出,Zr_(n)Al(n=4、6、8、12)团簇展现出较高的稳定性,适于作为幻数团簇的潜在候选。此外,还深入分析了Zr_(n)Al团簇的电子局域化函数(ELF)、态密度(DOS)以及磁矩。研究发现,Zr-Al和Zr-Zr原子间存在金属键相互作用。Zr_(n)Al(n=2~12)团簇的磁矩均表现出磁性,在n=2、3、4、10、12时团簇的磁矩相对较大,均为3μ_(B),其余尺寸团簇的磁矩基本上稳定在1μ_(B)左右,且未观察到磁矩猝灭现象;根据Mülliken布居数分析,团簇的总磁矩主要来源于锆原子的贡献,其中锆原子的磁矩主要由其4d轨道电子决定。
This study systematically screened the structures of small-sized Zr_(n)Al(n=2-12)clusters by employing density functional theory combined with the particle swarm optimization algorithm,successfully identifying their lowest-energy configurations.The results indicate that as the number of zirconium(Zr)atoms in the clusters increases,their geometries progressively evolve towards three-dimensional structures.At n=9,the clusters begin to adopt cage-like geometries,with the lowest-energy structure of Zr_(12)Al exhibiting a 20-faced icosahedral configuration of Ih symmetry.Stability assessments reveal that Zr_(n)Al clusters with n=4,6,8,12 demonstrate higher stability,suggesting their potential as magic number clusters.Additionally,this study provides an indepth analysis of the electronic localization function(ELF),density of states(DOS),and magnetic moments of the Zr_(n)Al clusters.The findings reveal the presence of metallic bonding interactions between Zr-Al and Zr-Zr atoms.All Zr_(n)Al clusters(n=2-12)exhibit magnetic properties,with relatively high magnetic moments of 3μ_(B) observed for n=2,3,4,10,12,while the magnetic moments of clusters with other sizes remain stable at approximately 1μ_(B),without evidence of magnetic moment quenching.Mülliken population analysis shows that the total magnetic moment of the clusters predominantly originates from the Zr atoms,with the magnetic moment of Zr primarily attributed to its 4d orbital electrons.
作者
杜燕
甘湘滨
田雨豪
张扬果儿
崔秀花
吉旭
DU Yan;GAN Xiangbin;TIAN Yuhao;ZHANG Yangguoer;CUI Xiuhua;JI Xu(Xinjiang Key Laboratory of Solid State Physics and Devices,School of Physical Science and Technology,Xinjiang University,Urumqi 830017,Xinjiang,China)
出处
《化学研究》
2026年第2期121-129,共9页
Chemical Research
基金
新疆维吾尔自治区自然科学基金项目(2025D01C43)
新疆大学大学生创新训练计划(202210755108,202310755098)。
