内含式化合物X@Al_(12)P_(12)的结构与稳定性研究  

Structure and Stability of Endohedral Complexes X@Al_(12)P_(12)

作　　者：武海顺[1] 张竹霞[1] 

机构地区：[1]山西师范大学材料化学研究所,临汾041004

出　　处：《化学学报》2005年第11期973-978,i001,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20341005)资助项目.

摘　　要：采用B3LYP/6.31G*方法,对内含式化合物X@AJ12P12(X=Li0/+,Na0/+,K0/+,Be0/2+,Mg0/2+,Ca0/2+,H和He)的不同对称性构型进行计算,讨论其最稳定构型的几何参数、布居分析、偶极矩、电离势、包含能、频率、HOMO-LUMO能隙和自旋密度.发现X@Al12P12化合物中,客体X=Na0/+,K0/+,Mg和He几乎处在笼的中心,Be和Ca0/2+处在中心附近0.033nm的半径内,Li0/+,Be2+,Mg2+和H很大程度上偏离笼的中心位置.大部分金属内含式化合物的C3对称性构型稳定.Li0/+,Be0/2+,Mg2+,Ca2+和H与其它离子相比更易嵌入笼内形成稳定的内含式化合物.Using quantum chemistry methods B3LYP/6-31G* to optimize endohedral clusters X@Al12P12 (X=Li0/+, Na0/+, K0/+, Be0/2+, Mg0/2+, Ca0/2+, H and He), the geometries with the lowest energy were achieved. The geometries, natural bond orbital, dipole moment, adiabatic ionization potential, inclusion energies, vibrational frequency, HOMO-LUMO energy gap and spin density were discussed at the same time. The calculations predict that X=Ne0/+, K0/+, Mg and He are nearly located at the center of the cage, and Be and Ca0/2+ lie in less than 0.033 mn departure from the center. Li0/+, Be2+, Mg2+ and H dramatically deviate from the center. The conformations with C-3-symmetry are favored in energies. Al12P12 will prefer to enclose Li0/+, Be0/2+, Mg2+, Ca2+ and H in it as compared to others.

关 键 词：X@Al12P12 稳定性 化学结构 内含式化合物 富勒烯 计算方法 偶极矩 自旋密度 电弧熔化法 

分 类 号：O614[理学—无机化学]