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Pseudorotaion in cyclooctane, using spherical conformational landscape model
Computational and Theoretical Chemistry ( IF 2.8 ) Pub Date : 2020-05-19 , DOI: 10.1016/j.comptc.2020.112845
Nader Sakhaee , Sahar Sakhaee , Akbar mobaraki

Medium sized rings and even small cyclic molecules have always challenged our static insights on them. They have thus forced us to propose models with conformers, connected in terms of energy and interconversions. The wheel-model of Lipnick et al. as well as the onion models of Hendrickson et al. are among the most sensible and sophisticated responses to such a demand. Here, DFT-ωb97xd/ 6–311 + G* computations confirmed by MP2/aug cc-pVTZ computations were used to fully investigate the energy, vibrations and full dynamics of 24 conformers. Then spherical conformational landscape SCL model was used to plot the conformational dynamics in cyclooctane for the first time. Classifications were done by a close inspection of the whole cast of conformers in cyclooctane, cyclopentane and cyclohexane. The fluxional Twist/Boat T/B ring coordinates were found to be a common feature in all the cyclic molecules studied. A new pictorial notion is suggested to present twist and boat conformers for all cyclic molecules in a generic sense. The simple, precise and universal conformational types presented here, unifies our perception of conformational dynamics in cyclic molecules, and paves the path towards a better analysis of cyclic motifs in natural products and bio-functional conformers.



中文翻译:

使用球形构象景观模型的环辛烷中的假七七

中型环甚至小环状分子一直挑战我们对它们的静态见解。因此,它们迫使我们提出具有能量和互转换相关的构象模型。Lipnick等人的车轮模型。以及Hendrickson等人的洋葱模型。是对这种需求最明智,最复杂的回应之一。在这里,通过MP2 / aug cc-pVTZ计算确认的DFT-ωb97xd/ 6-311 + G *计算被用来全面研究24个构象异构体的能量,振动和全动态。然后首次使用球形构象景观SCL模型绘制环辛烷中的构象动力学。通过仔细检查环辛烷,环戊烷和环己烷中的全部构象异构体进行分类。发现通量Twist / Boat T / B环坐标是所有研究的环状分子的共同特征。建议使用一种新的图形概念,以一般意义呈现所有环状分子的扭曲和船形构象。这里介绍的简单,精确和通用的构象类型,统一了我们对环状分子构象动力学的认识,并为更好地分析天然产物和生物功能构象异构体中的环状图案铺平了道路。

更新日期:2020-05-19
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