高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (9): 1521.

• 研究论文 • 上一篇    下一篇

Na-噻吩荷移配合物弱相互作用的理论研究

张翀1, 步宇翔1,2,3   

  1. 1. 曲阜师范大学化学系, 曲阜 273165;
    2. 山东大学教育部胶体与界面化学重点实验室;
    3. 山东大学理论化学研究所, 济南 250100
  • 收稿日期:2000-06-09 出版日期:2001-09-24 发布日期:2001-09-24
  • 通讯作者: 步宇翔(1962年出生),男,博士,教授,博士生导师,从事电荷转移机制及荷移分子功能性调控研究.
  • 基金资助:

    国家自然科学基金(批准号:29973022);高等院校国家重点实验室访问学者基金;山东省自然科学基金(批准号:98B04023)资助

Theoretical Study on the Weak-interaction of Thiophene-Na Charge Transfer Complex with Density Functional Theory

ZHANG Chong1, BU Yu-Xiang1,2,3   

  1. 1. Department of Chemistry Qufu Normal University, Qufu 273165, China;
    2. Key Laboratoryof Colloidand Interface Chemistryof Educational Ministry;
    3. Institute of Theoretical Chemistry, Shandong University, Jinan 250100, China
  • Received:2000-06-09 Online:2001-09-24 Published:2001-09-24

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摘要： 利用B3LYP法在6-311+G*水平上研究了Na-噻吩体系可能存在的3种Na-噻吩复合物A,B和C分子结构.结果表明:Na-噻吩体系存在2个能量极小结构A和C;结构B未得到证实.结构A中,Na的3s1电子直接和噻吩杂环的所有重原子进行弱相互作用形成一个具有Cs对称性的金属有机复合物;结构C中,Na原子的3s1电子主要通过和与S原子不直接相连的C2和C3进行弱相互作用,因而在原有的大π键基础上形成一个新的大π键,其结构为C2v对称性.结构A较结构C稳定78.0kJ/mol.结构A中的Na—S之间的距离为0.407nm,键角∠CSC为91°,金属Na和噻吩之间的弱相互作用使整个噻吩分子平面稍微变形,S原子向Na所在的一侧稍微偏离C环平面.结构C中Na-S之间的距离为0.825nm,∠CSC为91°,金属Na原子和杂环中所有的原子在同一个平面内.在B3LYP、MP2、MP3和MP4水平上,分别用6-311+G*和6-311++G**基组精确计算了最稳定结构A的结合能ΔE为8.3～10.9kJ/mol.

关键词: Na-噻吩, abinitio, B3LYP, 结合能&Delta, E, 分子间弱相互作用

Abstract: Geometric parameters of three Na thiophene complexes(A, B, C) and the ground state bonding energy Δ Ehave been determined at the B3LYP/6-311+G * level in this paper. The results have indicated that there are two energy minimum points on the potential energy surface which correspond to two stable structures(Aand C) and geometry Bdoes not exist. Of the two structures, the geometry Acorresponds to the ground state in which R (Na-S)=0.407 nm and ∠CSC=91°, structure Cwith R (Na-S) of 0.825 nm and ∠CSCof 91° is energetically higher than structure Aby 78.0 kJ/mol. For structure A, 3s orbital of Na atom directly interacts with Π56 bonding of the thiophene molecule, resulting in a new weak interaction organometallic complex with Cs symmetry. For the structure C, 3 s orbital of Na mainly interacts with the two Catoms apart from Satom in thiophene, forming a new Π67 bonding derived from original Π56 bonding of thiophene, but the structure Chas C2v symmetry. There is also a slight geometry deformation of thiophene molecule plane for structure Ain which the Sis slightly apart from cyclic Cplane. The bonding energies Δ Eaccurately calculated using by MP2, MP3, MP4 and B3LYPmethods with 6-311+G * and 6-311++G ** basis sets for the ground state structure Afall within 8.3-10.9 kJ/mol.

Key words: Na-thiophene complex, ab initio, B3LYP, Binding energy, Intermolecular weak interaction

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