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胞嘧啶与单壁碳纳米管之间的非共价相互作用:通过π…π堆积和协同的C-H…π/N-H…π作用对复合物曲率的依赖性

Noncovalent interactions between cytosine and SWCNT: curvature dependence of complexes via pi...pi stacking and cooperative CH...pi/NH...pi.

作者信息

Wang Yixuan, Bu Yuxiang

机构信息

Department of Natural Science, Albany State University, Albany, Georgia 31705, USA.

出版信息

J Phys Chem B. 2007 Jun 14;111(23):6520-6. doi: 10.1021/jp0700433. Epub 2007 May 18.

Abstract

Fragments of C24H12, adapted from a variety of armchair [(n,n), (n = 5, 7, and 8)] and zigzag [(m,0) (m = 8, 10, and 12)] single-walled carbon nanotube (SWCNT), are used to model corresponding SWCNTs with different diameters and electronic structures. The parallel binding mainly through pi...pi stacking interaction, as well as the perpendicular binding via cooperative NH...pi and CH...pi between cytosine and the fragments of SWCNT have been extensively investigated with a GGA type of DFT, PW91LYP/6-311++G(d,p). The eclipsed tangential (ET) conformation with respect to the six-membered ring of cytosine and the central ring of SWCNT fragments is less stable than the slipped tangential (ST) conformation for the given fragment; perpendicular conformations with NH2 and CH ends have higher negative binding energy than those with NH and CH ends. At PW91LYP/6-311++G(d,p) level, two tangential complexes are less bound than perpendicular complexes. However, as electron correlation is treated with MP2/6-311G(d,p) for PW91LYP/6-311++G(d,p) optimized complexes, it turns out there is an opposite trend that two tangential complexes become more stable than three perpendicular complexes. This result implies that electron correlation, a primary source to dispersion energy, has more significant contributions to the pi...pi stacking complexes than to the complexes via cooperative NH...pi and CH...pi interactions. In addition, it was found for the first time that binding energies for two tangential complexes become more negative with increasing nanotube diameter, while those for three perpendicular complexes have a weaker dependence on the curvature; i.e., binding energies are slightly less and less negative. The performance of a novel hybrid DFT, MPWB1K, was also discussed.

摘要

从各种扶手椅型[(n,n),(n = 5、7和8)]和锯齿型[(m,0) (m = 8、10和12)]单壁碳纳米管(SWCNT)改编而来的C24H12片段,用于模拟具有不同直径和电子结构的相应SWCNT。主要通过π…π堆积相互作用的平行结合,以及胞嘧啶与SWCNT片段之间通过协同的NH…π和CH…π的垂直结合,已使用GGA类型的DFT,PW91LYP/6 - 311++G(d,p)进行了广泛研究。对于给定片段,相对于胞嘧啶的六元环和SWCNT片段的中心环的重叠切向(ET)构象比滑移切向(ST)构象不稳定;具有NH2和CH末端的垂直构象比具有NH和CH末端的垂直构象具有更高的负结合能。在PW91LYP/6 - 311++G(d,p)水平下,两个切向复合物的结合比垂直复合物弱。然而,当对PW91LYP/6 - 311++G(d,p)优化的复合物用MP2/6 - 311G(d,p)处理电子相关时,结果表明存在相反的趋势,即两个切向复合物比三个垂直复合物更稳定。该结果表明,作为色散能的主要来源的电子相关,对π…π堆积复合物的贡献比对通过协同NH…π和CH…π相互作用形成的复合物的贡献更大。此外,首次发现两个切向复合物的结合能随着纳米管直径的增加而变得更负,而三个垂直复合物的结合能对曲率的依赖性较弱;即结合能的负值略有减小。还讨论了一种新型混合DFT,MPWB1K的性能。

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