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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (11): 973-978. 上一篇    下一篇

研究论文

内含式化合物X@Al12P12的结构与稳定性研究

武海顺*，张竹霞   

  1. (山西师范大学材料化学研究所　临汾 041004)
  • 投稿日期:2004-08-31 修回日期:2005-02-03 发布日期:2010-12-10
  • 通讯作者: 武海顺

Structure and Stability of Endohedral Complexes X@Al12P12

WU Hai-Shun*, ZHANG Zhu-Xia   

  1. (Institute of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004)
  • Received:2004-08-31 Revised:2005-02-03 Published:2010-12-10
  • Contact: WU Hai-Shun

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采用B3LYP/6-31G*方法, 对内含式化合物X@Al12P12 (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0.033 nm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.

关键词: 内含式化合物, 偶极矩, 包含能, HOMO-LUMO能隙, 自旋密度

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＝Na0/＋, K0/＋, Mg and He are nearly located at the center of the cage, and Be and Ca0/2＋ lie in less than 0.033 nm departure from the center. Li0/＋, Be2＋, Mg2＋and H dramatically deviate from the center. The conformations with C3-symmetry are favored in energies. Al12P12 will prefer to enclose Li0/＋, Be0/2＋, Mg2＋, Ca2＋and H in it to others.

Key words: endohedral complex, dipole moment, inclusion energy, HOMO-LUMO energy gap, spin density