基于密度泛函理论的5~10元瓜环结构参数与前线轨道的计算

doi:10.19596/j.cnki.1001-246x.7631

摘要/Abstract

摘要： 在气相环境中，使用密度泛函理论（DFT）优化由n个苷脲单元组成的瓜环[n]（CB[n]）（n=5~10），并使用密度泛函（DFT）概念指数和Multiwfn软件包计算和分析CB[n]的结构参数、前线轨道能量和化学稳定性.结果表明：α-N结构最稳定，α=O、γ-γ、γ-H和β-H（2）结构的化学稳定性较差；以CB[6]为界，主要二面角的变化呈现中心对称的形式；随着苷脲单元n的增加，CB[n]的端口直径、空腔直径和圆外径线性增大；前线轨道E_HOMO、E_LUMO值及E_LUMO-E_HOMO值逐渐降低，化学活性逐渐增强、稳定性逐渐减弱；端口O原子是最大的亲电活性位点，LUMO的电子云分布主要与H原子有关，且次甲基H原子对LUMO电子云的贡献最大；次甲基C原子、亚甲基C原子和指向CB[n]端口方向的亚甲基H原子对LUMO的电子云分布具有抑制作用，抑制能力的大小为指向CB[n]端口方向的亚甲基H原子>亚甲基C原子>次甲基C原子.为研究瓜环的超分子组装提供理论依据.

关键词: 瓜环[n], 密度泛函理论, Multiwfn软件包, 结构参数, 前线轨道

Abstract: In gas phase, structure of cucurbituril (CB[n],n=5-10) composed of n glycoluril units was optimized by density functional theory (DFT). Structural parameters, frontier orbital energy levels and chemical stability of CB[n](n=5-10) were calculated and analyzed with conceptual DFT reactivity index and Multiwfn wave function analyzer. It showed that structure of C-N bond is most stable, chemical stability of α=O, γ-γ, γ-H and β-H(2) is poor. Change of part bond angle is bounded by CB[6], and change of main dihedral angle exhibits symmetrical. Port diameter, cavity diameter and outer diameter of CB[n](n=5-10) tend to increase linearly with increase of number of glycoluril units. E_HOMO, E_LUMO and E_LUMO-E_HOMO of CB[n](n=5-10) reduced, their chemical activity increased and stability decreased with increase of number of glycoluril units. The largest electrophilic active sites are located at port O atoms. Electron cloud distribution of LUMO is mainly related to H atoms,and contribution of methine H atom to LUMO electron cloud is the largest. Methine C atom, methylene C atom, and methylene atom H in direction of CB[n] port have an inhibitory effect on electron cloud distribution of LUMO. Inhibitory capacity is methylene H atom in direction of CB[n] > methylene C atom > methine C atom. It provides theoretical basis for study of supramolecular assembly of cucurbituril.

Key words: cucurbituril[n], density functional theory, Multiwfn wave function analyzer, structural parameter, frontier orbit

中图分类号:

O561.1

林艳, 刘芸, 彭清维, 魏晓楠, 唐延林. 基于密度泛函理论的5~10元瓜环结构参数与前线轨道的计算[J]. 计算物理, 2018, 35(2): 221-229.

LIN Yan, LIU Yun, PENG Qingwei, WEI Xiaonan, TANG Yanlin. Calculation of Structural Parameters and Frontier Orbital of Cucurbituril (5-10) with Density Functional Theory[J]. CHINESE JOURNAL OF COMPUTATIONAL PHYSICS, 2018, 35(2): 221-229.

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