采用密度泛函方法研究Ce_(3)Se_(n)^(+/0/-)(n=1~12)团簇的结构、稳定性及电子性质

Structure,Stability and Electronic Properties of Ce_(3)Se_(n)^(+/0/-)(n=1~12):Density Functional Theory Investigation

通过ABCluster全局搜索技术结合TPSSh密度泛函的方法研究了Ce_(3)Se_(n)^(+/0/-)(n=1~12)团簇的基态构型及结构演化模式。该团簇的结构演化模式主要分为两个阶段一个节点,即n≤3时,以Ce_(3)组成的三角形作为结构骨架,Se原子逐一吸附其上;当n=4时,Ce_(3)Se_(4)^(+/0/-)形成了稳定的不完整立方烷结构;n>4时,以Ce_(3)Se_(4)不完整立方烷结构成为新的结构骨架,Se原子逐个吸附其上。同时模拟了阴离子团簇的光电子能谱(PES),计算了团簇平均键能(ABE)、HOMO-LUMO能隙(E_(gap))和二阶能量差分(Δ^(2)E)。结果表明,Ce_(3)Se_(4)^(+)团簇表现出卓越的化学稳定性和热力学稳定性,在半导体纳米构筑模块材料领域具有潜在的应用价值。

The ground state configurations and structural evolution pattern of Ce_(3)Se_(n)^(+/0/-)(n=1~12)clusters were theoretically investigated by the ABCluster global search technique combined with the TPSSh density functional method.The evolutionary mode of the clusters can be delineat-ed into two distinct stages and a singular node,that is,when n≤3,the triangle composed of Ce_(3)acts as the structural skeleton,on which Se atoms are continuously attached;when n=4,Ce_(3)Se_(4)^(+/0/)-forms a stable incomplete cubane-like structure and when n>4,Ce_(3)Se_(4)with incomplete cubane-like structure acts as new structural basis,on which Se atoms are continuously attached.The photoelectron spectroscopy(PES)of anion cluster was sim-ulated.The average binding energy(ABE),HOMO-LUMO energy gap(Egap)and second-order energy difference(Δ^(2)E)of the clusters were calculat-ed.Through comparison and analysis,it is evident that Ce_(3)Se_(4)^(+)cluster reveals excellent chemical and thermodynamic stability,which means it has potential application value in the field of preparation of semiconductor nanostructured module materials.