Marsusi Farah, Mirabbaszadeh Kavoos
Department of Physics, Amirkabir University of Technology, PO Box 15875-4413, Tehran, Iran.
J Phys Condens Matter. 2009 May 27;21(21):215303. doi: 10.1088/0953-8984/21/21/215303. Epub 2009 May 1.
The stability, optimized structure, and electronic gap of four diamondoid complexes, adamantane, C(10)H(16), diamantane, C(14)H(20), triamantane, C(18)H(24) and the T(d)-symmetry isomer of pentamantane, C(26)H(32), incorporating cage-centered small atoms and ions (X@cage, where X = H(+), Li(0,+), Be(0,+,2+), Na(0,+), Mg(0,2+), He, Ne, and F(-)) have been studied at the B3LYP hybrid level of theory. All adamantane complexes, except those encapsulating H(+) and Mg, are endohedral minima. In contrast no diamantane complexes are minima. A wide variety of atoms and ions can be encapsulated by triamantane and pentamantane molecules. The complexes are more stable for smaller and more highly charged metallic guest species. The electronic HOMO-LUMO gaps of diamondoid complexes are significantly affected by the inclusion of charged particles. The stability of the structures, the amount of the charges which are transferred between small particles and diamondoids cages, and the change in the HOMO-LUMO gaps of diamondoids are nearly the same for the corresponding possible complexes. All these features mostly depend on the charge, the size and the type of the encapsulated particle, and not on the type of diamondoid.
在B3LYP杂化理论水平下，研究了四种类金刚石配合物（金刚烷，C(10)H(16)；二聚金刚烷，C(14)H(20)；三聚金刚烷，C(18)H(24)；以及五聚金刚烷的Td对称异构体，C(26)H(32)），它们包含笼中心的小原子和离子（X@笼，其中X = H(+)、Li(0,+)、Be(0,+,2+)、Na(0,+)、Mg(0,2+)、He、Ne和F(-)）的稳定性、优化结构和电子能隙。除了包封H(+)和Mg的那些配合物外，所有金刚烷配合物都是内包合物极小值。相比之下，没有二聚金刚烷配合物是极小值。三聚金刚烷和五聚金刚烷分子可以包封多种原子和离子。对于较小且电荷更高的金属客体物种，配合物更稳定。类金刚石配合物的电子HOMO-LUMO能隙受带电粒子的纳入显著影响。对于相应的可能配合物，类金刚石结构的稳定性、小粒子与类金刚石笼之间转移的电荷量以及类金刚石HOMO-LUMO能隙的变化几乎相同。所有这些特征主要取决于包封粒子的电荷、大小和类型，而不取决于类金刚石的类型。
