AlnCl(n=2-14)团簇结构与电子性质的理论研究

运用卡里普索(CALYPSO)结构预测方法，在杂化密度泛函B3LYP/6-311G+(d)基组水平上，对AlnCl(n=2-14)团簇的几何结构与电子性质进行优化计算，并讨论了团簇的平均结合能、能隙、二阶能量差分、电离能、亲和能以及电子自然布局和极化率。研究结果表明：AlnCl(n=2-14)团簇的基态构型由简单平面几何结构向立体结构演化，形成Cl原子戴帽Aln-1Cl团簇结构；Cl原子的掺杂增大了Aln团簇的平均结合能；二阶能量差分、能隙、电离能、亲和能的变化表明Al7Cl是幻数团簇结构；团簇中的电荷总是由Al原子向Cl原子转移，原子之间的成键作用随着团簇尺寸的增大而增强。

Theoretical study on the structure and electronic properties of AlnCl(n=2-14) Clusters

The geometrical structure, stability and electronic properties of the AlnCl (n=2-14) clusters have been investigated by using the density functional theory (DFT) at B3LYP 6-311G+(d) level, based on the Crystal structure Analysis by Particle Swarm Optimization(CALYPSO). The binding energies, second-order energy difference, energy-gaps, vertical ionization potentials, vertical electronic affinities and the polarizations and natural population are also discussed. The calculated results indicate that: the most stable structures of AlnCl clusters develop from planar to three-dimensional structure; the Aln-1Cl structure capped with one Cl atom is the dominant growth behavior for different sized AlnCl clusters; the doping of Cl atom increases the binging energy of clusters; the second order energy difference, energy-gaps, vertical ionization potentials, vertical electronic affinities indicate that Al7Cl is the magic cluster. Charges always transfer from Al atoms to Cl atom in all sized AlnCl clusters, and the bonding interaction between atoms in clusters increase with the increasing cluster size.