吡咯与HCl和CHCl_3分子间Cl(C)—H…π型氢键的理论研究  

Theoretical Study of the Hydrogen Bonding between Pyrrole and HCl, CHCl_3

作　　者：史福强[1] 安静仪[1] 李文[1] 赵濉[1] 俞稼镛[1] 

机构地区：[1]中国科学院理化技术研究所,北京100101

出　　处：《化学学报》2004年第12期1171-1175,MJ06,共6页Acta Chimica Sinica

基　　金：国家重点基础研究规划 (No.G1 9990 2 2 5)资助项目

摘　　要：运用量子化学从头算 (abinitio)方法 ,采用 6 3 1G(d ,p)基组对吡咯和HCl单体进行优化 ,结果表明MP2 /6 3 1G(d ,p)计算结果与实验结果较吻合 .然后采用MP2 /6 3 1G(d ,p)方法对吡咯 HCl体系以及吡咯 CHCl3 体系的分子间Cl(C)—H…π型氢键进行了理论研究 ,并在MP2 /aug cc pVDZ水平计算了氢键作用能 .研究表明 ,吡咯与HCl分子和CHCl3 之间形成了Cl(C)—H…π型氢键 ,吡咯与HCl分子的氢键相互作用使HCl中H—Cl键长增加 ,振动频率减小了 14 9cm-1(红移 ) ;而吡咯与CHCl3 之间的相互作用使CHCl3 中的C—H键长减小 ,振动频率增加了 3 3cm-1(蓝移 ) .利用自然键轨道 (NBO)分析表明电荷发生转移 ,吡咯 HCl体系中HCl得到 0 0 15 5e ;吡咯 CHCl3 体系中CHCl3 得到 0 0 0 98e .Geometries of pyrrole and HCl monomers were calculated at HF/6-31G (d, p), MP2/6-31G (d, p) respectively. The outcome indicates that MP2/6-31G (d, p) is the better method. The structures, vibrational frequencies, and interaction energies of the hydrogen-bonding complexes between HCl, CHCl3 and pyrrole were examined using the Moller-Plesset (second order) theory. Full geometry optimization of these complexes were calculated using the 6-31G (d, p) basic sets. After BSSE (basic set superposition error) by the counterpoise method and ZPE correction, the interaction energies of the pyrrole-HCl (CHCl3) complexes were calculated at the MP2 level with the aug-cc-pVDZ basis set to be about -18.45 and -24.45 kJ/mol, respectively. The H-Cl and H-C stretching modes of complexes are red-shifted and blue-shifted relative to those of the monomer, respectively. Charge transfer of the two complexes is 0.0155e and 0.0098e, respectively.

关 键 词：吡咯 氯化氢 三氯甲烷 氢键 量子化学从头算 振动频率 

分 类 号：O621.13[理学—有机化学]