金属硼球烯VB40-团簇的结构、稳定性、光谱和键合:粒子群优化算法结合密度泛函理论研究
Structure,stability,spectra,and bonding of metalloborospherene VB40-clusters:A density functional study combining the particle swarm optimization algorithm
曾淑琼 1黄曦宇 1刘桂林 1黄予谦 1牛振威 1唐梅 2葛妮娜2
作者信息
- 1. 西南科技大学国防科技学院,绵阳 621010
- 2. 西南科技大学核废物与环境安全国防重点学科实验室,绵阳 621010
- 折叠
摘要
本文通过粒子群优化算法结合量子化学计算,对V掺杂硼团簇VB40-的各种候选结构进行了全局预测.对于VB40-团簇,我们预测2个能量最低的结构(结构Ⅰ和Ⅱ)为内嵌式金属硼球烯.结构Ⅰ具有C2v对称性,继承了B40(D2d对称性)的笼形结构,硼与钒的配位数为16,而结构Ⅱ之前未见报道.值得注意的是,新发现的结构Ⅱ有Cs对称性,有最高配位数,为20.基于这2种结构,本文利用分子轨道、Wiberg键级和电子局域函数分析了其电子性质.适应性自然密度划分与化学键分析表明,VB40-团簇(C2v对称性)的σ键和π键较好地继承了B40(D2d对称性)键的特征.此外,我们还模拟了光电子能谱、红外光谱、拉曼光谱和紫外可见光光谱,以便于后期的实验表征.
Abstract
Various candidate structures of V-doped boron clusters VB40-are predicted globally via the particle swarm optimization algorithm combining quantum chemistry calculations.For the VB40-clusters,the two low-est energy structures(C2v structure Ⅰ and Cs structure Ⅱ)are predicted to be endohedral metalloborospher-enes.Structure Ⅰ is well inherited in the cage geometry of D2d B40 with the vanadium coordination number of sixteen,while structure Ⅱ has not been reported before.Notably,the newly discovered structure Ⅱ has 20-fold coordination with the largest coordination state.Based on these two structures,electronic properties are analyzed by molecular orbitals,Wiberg bond order and electron localization function.The adaptive natural den-sity partitioning and chemical bond analysis indicate that both the σ and π bonds of the C2v VB40-cluster are well inherited in the D2d B40 bonding characteristics.In addition,photoelectron spectroscopy,infrared,Raman,and UV-Vis spectra are simulated to facilitate future experimental characterizations.
关键词
金属硼球烯/光电子能谱/CALYPSO/密度泛函理论Key words
Metalloborospherene/Photoelectron spectroscopy/CALYPSO/Density functional theory引用本文复制引用
基金项目
四川省自然科学基金(2022NSFSC1243)
四川省自然科学基金(2022NSFSC1826)
出版年
2024
国家科技期刊平台
NSTL
万方数据