芳香族环b[10]碳中伪Jahn-Teller效应的第一性原理路径积分蒙特卡罗研究

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
Anna H. James, Martina Kaledin* and Alexey L. Kaledin*, 
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引用次数: 0

摘要

人们对碳纳米结构重新产生了兴趣。最近在4.7 K下的实验测量和随后在0 K下基于第一原理的振动扩散蒙特卡罗模拟表明,芳香环[10]碳倾向于D5h的五边形结构,而不是规则的D10h十角形结构。这种对称性破缺是由二阶扬-泰勒效应(JTE)引起的,文献中对积云旋回[4m + 2]碳团簇进行了充分的描述。然而,在环[4m + 2]碳团簇中,特别是环[10]碳团簇中JTE的温度依赖性尚未得到系统的研究。在这项工作中,我们采用路径积分蒙特卡罗模拟第一原理推导的排列不变势能面(PES)来研究环[10]碳中的JTE作为温度的函数。PES在一组采样到D5h全球最小值以上~ 7.7 eV的τHCTH/cc-pVQZ能量上进行训练,并在局部调整到D5h全球最小值与D10h过渡态之间812 cm-1的高水平基准(其他人报道)。计算结果表明,在较低温度下,JTE表现出较强的JTE,在100 K时以D5h成分为主,而在300 K以上,JTE逐渐减弱,呈现出五角形的冲刷结构。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
First-Principles Path Integral Monte Carlo Studies of the Pseudo Jahn–Teller Effect in the Aromatic Cyclo[10]carbon

There has been renewed interest in carbon nanoscale structures. Experimental measurements at 4.7 K and subsequent first-principles-based vibrational diffusion Monte Carlo simulations at 0 K recently showed that the aromatic cyclo[10]carbon prefers a D5h pentagon-like structure to a regular D10h decagon. This symmetry breaking is due to the second-order Jahn–Teller effect (JTE) and has been amply described in the literature for the cumulenic cyclo[4m + 2]carbon clusters. Yet temperature dependence of the JTE in cyclo[4m + 2]carbon clusters in general and the cyclo[10]carbon in particular has not been studied systematically. In this work, we employ path integral Monte Carlo simulations on a first-principles-derived permutationally invariant potential energy surface (PES) to examine the JTE in cyclo[10]carbon as a function of temperature. The PES was trained on a set of τHCTH/cc-pVQZ energies sampled up to ∼7.7 eV above the D5h global minimum and locally adjusted to a high-level benchmark (reported by others) of the 812 cm–1 electronic energy difference between the D5h global minimum and the D10h transition state. The calculations show a strong JTE at lower temperatures with a dominant D5h composition at 100 K and a gradually diminishing JTE at higher temperatures with a washed-out pentagonal structure above 300 K.

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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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