夹心双核茂合物Cp_2TM_2(TM=Zn/Cu/Ni)电子结构和储氢性能的第一性原理研究  

First-principles Study on the Electronic Structure and Hydrogen Storage Properties of Sandwich-type Dimetallocenes

作　　者：安博[1] 

机构地区：[1]渭南师范学院物理与电气工程学院,渭南714000

出　　处：《人工晶体学报》2013年第7期1470-1474,1480,共6页Journal of Synthetic Crystals

基　　金：陕西省科技厅科研资助项目(2012JM6019);陕西省教育厅科研资助项目(12JK0991)

摘　　要：使用基于密度泛函理论(DFT)的DMOL3程序包,研究了双金属茂合物Cp2TM2(TM=Zn/Cu/Ni)的几何结构、电子结构和储氢性能。结果表明:不同夹心原子对体系几何结构的影响微弱;Zn/Cu/Ni茂合物的电子局域态密度(LDOS)在费米能级(EF)处起主要作用的是d轨道电子;随夹心原子Zn/Cu/Ni原子序数的降低,其茂合物最低非占据轨道和最高占据轨道的差值(LUMO-HOMO)逐渐降低。Zn/Cu/Ni茂合物均可吸附8个H2分子,其平均吸附能分别为0.802 eV/H2(Cp2Zn2)、0.422 eV/H2(Cp2Cu2)和0.182 eV/H2(Cp2Ni2),储氢容量分别达到6.2wt%(Cp2Zn2)、6.3wt%(Cp2Cu2)和6.5wt%(Cp2Ni2)。With respect to first-principles calculation,the electronic structure and ability of absorbing hydrogen molecule of the dimetallocene（C5H5） 2TM2（TM = Zn/Cu/Ni） was investigated.The results indicated that doped atoms have little effect on the geometrical structure of dimetallocenes.The peak position of Zn / Cu / Ni atoms ＇ LDOS changes indistinctively on EF,and the d electron orbit has the principal affect.As the atomic number decreasing,the LUMO-HOMO gap of Zn / Cu / Ni dimetallocenes decreased.These compounds could adsorb up to eight hydrogen molecules,the binding energy is 0.802 eV / H2 for Cp2Zn2,0.422 eV/H2 for Cp2Cu2 and 0.182 eV / H2 for Cp2Ni2 respectively.The corresponding gravimetric hydrogen-storage capacity is 6.2wt% for Cp2Zn2,6.3wt% for Cp2Cu2 and 6.5wt% for Cp2Ni2 respectively.

关 键 词：双金属茂合物 电子结构 储氢 第一性原理 

分 类 号：TM22[一般工业技术—材料科学与工程]