Few-femtosecond electronic and structural rearrangements of CH4+ driven by the Jahn–Teller effect

Kristina S. Zinchenko, Fernando Ardana-Lamas, Valentina Utrio Lanfaloni, Nicholas Monahan, Issaka Seidu, Michael S. Schuurman, Simon P. Neville, Hans Jakob Wörner
{"title":"Few-femtosecond electronic and structural rearrangements of CH4+ driven by the Jahn–Teller effect","authors":"Kristina S. Zinchenko, Fernando Ardana-Lamas, Valentina Utrio Lanfaloni, Nicholas Monahan, Issaka Seidu, Michael S. Schuurman, Simon P. Neville, Hans Jakob Wörner","doi":"10.1063/4.0000217","DOIUrl":null,"url":null,"abstract":"The Jahn–Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE in stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of CH4+ from the initial Td geometry to a nominal C2v relaxed structure range from 1.85 fs over 10 ± 2 fs to 20 ± 7 fs. Here, by combining element-specific attosecond transient-absorption spectroscopy and quantum-dynamics simulations, we show that the initial electronic relaxation occurs within 5 fs and that the subsequent nuclear dynamics are dominated by the Q2 scissoring and Q1 symmetric stretching modes, which dephase in 41 ± 10 fs and 13 ± 3 fs, respectively. Significant structural relaxation is found to take place only along the e-symmetry Q2 mode. These results demonstrate that CH4+ created by ionization of CH4 is best thought of as a highly fluxional species that possesses a long-time-averaged vibrational distribution centered around a D2d structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn–Teller driven non-adiabatic dynamics in other more complex systems.","PeriodicalId":21992,"journal":{"name":"Structural Dynamics","volume":"3 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Structural Dynamics","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1063/4.0000217","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0

Abstract

The Jahn–Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE in stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of CH4+ from the initial Td geometry to a nominal C2v relaxed structure range from 1.85 fs over 10 ± 2 fs to 20 ± 7 fs. Here, by combining element-specific attosecond transient-absorption spectroscopy and quantum-dynamics simulations, we show that the initial electronic relaxation occurs within 5 fs and that the subsequent nuclear dynamics are dominated by the Q2 scissoring and Q1 symmetric stretching modes, which dephase in 41 ± 10 fs and 13 ± 3 fs, respectively. Significant structural relaxation is found to take place only along the e-symmetry Q2 mode. These results demonstrate that CH4+ created by ionization of CH4 is best thought of as a highly fluxional species that possesses a long-time-averaged vibrational distribution centered around a D2d structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn–Teller driven non-adiabatic dynamics in other more complex systems.
由贾恩-泰勒效应驱动的 CH4+ 几飞秒电子和结构重排
扬-泰勒效应(JTE)是了解各种分子和材料的物理和化学特性的核心。虽然对 JTE 在物质静态特性中的表现形式研究相对较多,但对 JTE 引发的动力学研究仍处于起步阶段,这主要是由于其超高速和非绝热性质。例如,据报道,CH4+ 从初始 Td 几何结构变形为标称 C2v 松弛结构的时间尺度从 1.85 fs 到 10 ± 2 fs 再到 20 ± 7 fs 不等。在这里,通过结合特定元素的阿秒瞬态吸收光谱和量子力学模拟,我们发现最初的电子弛豫发生在 5 fs 内,随后的核动力学由 Q2 剪切和 Q1 对称拉伸模式主导,它们分别在 41 ± 10 fs 和 13 ± 3 fs 内相消。发现只有沿 e 对称 Q2 模式才会发生显著的结构弛豫。这些结果表明,CH4 电离产生的 CH4+ 最好被视为一种高通量物种,它具有以 D2d 结构为中心的长时平均振动分布。我们工作中展示的方法为理解其他更复杂系统中的扬-泰勒驱动非绝热动力学提供了指导。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
自引率
0.00%
发文量
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信