Do Molecular Geometries Change Under Vibrational Strong Coupling?,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Do Molecular Geometries Change Under Vibrational Strong Coupling?
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2024-07-23 , DOI: 10.1021/acs.jpclett.4c01810
Thomas Schnappinger ₁ , Markus Kowalewski ₁

Affiliation

As pioneering experiments have shown, strong coupling between molecular vibrations and light modes in an optical cavity can significantly alter molecular properties and even affect chemical reactivity. However, the current theoretical description is limited and far from complete. To explore the origin of this exciting observation, we investigate how the molecular structure changes under strong light–matter coupling using an ab initio method based on the cavity Born–Oppenheimer Hartree–Fock ansatz. By optimizing H₂O and H₂O₂ resonantly coupled to cavity modes, we study the importance of reorientation and geometric relaxation. In addition, we show that the inclusion of one or two cavity modes can change the observed results. On the basis of our findings, we derive a simple concept to estimate the effect of the cavity interaction on the molecular geometry using the molecular polarizability and the dipole moments.

中文翻译：

振动强耦合下分子几何形状会发生变化吗？

正如开创性实验所表明的那样，光学腔中分子振动和光模式之间的强耦合可以显着改变分子特性，甚至影响化学反应性。然而，目前的理论描述是有限的并且远不完整。为了探索这一令人兴奋的观察的起源，我们使用基于腔 Born-Oppenheimer Hartree-Fock ansatz 的从头计算方法研究了强光-物质耦合下分子结构如何变化。通过优化与腔模式共振耦合的 H ₂ O 和 H ₂ O ₂ ，我们研究了重新定向和几何松弛的重要性。此外，我们还表明，包含一种或两种腔模式可以改变观察到的结果。根据我们的发现，我们得出了一个简单的概念，利用分子极化率和偶极矩来估计空腔相互作用对分子几何形状的影响。

更新日期：2024-07-23

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南