摘要
结合卡利普索结构预测程序和密度泛函理论的第一性原理计算,详细研究了M_(2)(M=Li,Na,K)掺杂B^(-)_(20)团簇体系的几何结构、电子、热力学和光谱特性.结构分析表明,碱金属原子的掺杂完全改变了原B^(-)_(20)团簇几何结构.Li_(2)B^(-)_(20)和Na_(2)B^(-)_(20)团簇的全局极小结构拥有相似几何构型,结构由一个管(两个B_(9)环包含两个B)和管异侧的两个M原子构成.K_(2)B^(-)_(20)团簇的全局极小结构为高对称性的管状结构,掺杂的两个K原子分居两个B10环构成管的两侧.基于上述全局极小结构,分析了体系的电子特性(电荷转移和磁性)和热力学特性(定容热容和标准熵).最后,基于Multiwfn程序,拟合出了体系的光电子能谱、红外和拉曼光谱.本文工作为M_(2)B^(-)_(20)(M=Li,Na,K)团簇的实验和理论研究提供了指导和帮助.
The geometric,electronic,thermodynamic and spectral properties of M_(2)(M=Li,Na,K)-doped B^(-)_(20) cluster systems are studied in detail by using Calypso structure prediction program and first‑principles calculations of density functional theory.The structural analysis showed that the alkali metal atoms doping significantly changes the original structures of B^(-)_(20) cluster.The global minimal structure of Li_(2)B^(-)_(20) and Na_(2)B^(-)_(20) are composed of two borons-centered eighteen-membered drum with two M atoms on the both sides.K_(2)B^(-)_(20) cluster constructed by the combination of two ten-member rings showed a tubular geometry with two K atoms located at two sides of the tube.Based on these structures,some electronic properties including charge transfer and magnetic moments,and thermodynamic properties via the standard molar heat capacity and standard molar thermal entropy were analyzed,respectively.In addition,to provide a theoretical basis for the identification and confirmation of studied clusters,the PES,IR,Raman spectra with different and meaningful characteristic peaks were simulated based on the Multiwfn program.The work in this paper provides guidance and help for the experimental and theoretical study of M_(2)B^(-)_(20)(M=Li,Na,K)clusters.
作者
刘帅志
崔淑琦
燕新杰
张颖堃
陶俊龙
李成刚
崔颍琦
邵琴琴
LIU Shuai-Zhi;CUI Shu-Qi;YAN Xin-Jie;ZHANG Ying-Kun;TAO Jun-Long;LI Cheng-Gang;CUI Ying-Qi;SHAO Qin-Qin(School of Physics and Electronic Engineering,Zhengzhou Normal University,Zhengzhou 450041,China;School of General Education,Wuchang University of Technology,Wuhan 430223,China;School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China)
出处
《四川大学学报（自然科学版）》
CAS
CSCD
北大核心
2024年第2期113-120,共8页
Journal of Sichuan University(Natural Science Edition)
基金
国家自然科学基金(11904328,12104416)
河南省大学生创新创业训练计划项目(S202312949011)
郑州师范学院本科教学改革研究项目(JXGG-20773)。
