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回复“评论:‘分离振动极化激元 2D-IR 传输光谱’”。

Reply to "Comment on: 'Isolating Vibrational Polariton 2D-IR Transmission Spectra'".

机构信息

Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan48109, United States.

Department of Physics, University of Michigan, 430 Church Avenue, Ann Arbor, Michigan48109, United States.

出版信息

J Phys Chem Lett. 2023 Feb 2;14(4):1046-1051. doi: 10.1021/acs.jpclett.2c02823.

Abstract

In a Comment on our recent Letter, the authors take issue with our method of refining 2D-IR transmission spectra to remove a background contribution that arises from nonpolaritonic molecules in the cavity. In our response to their Comment, we describe how our approach was motivated by the previous work of the authors, and we present a spatially dependent molecule-cavity Tavis-Cummings model that can account for the significant response from localized molecules with nonzero oscillator strengths. The telltale signature of the localized molecule response is the spectral diffusion dynamics of the bare W(CO) molecules in the polar butyl acetate solvent. Inhomogeneous broadening is absent from polaritonic states due to the extreme degree of exchange narrowing in coupling very large numbers of molecules to a cavity mode.

摘要

在对我们最近的信件的评论中,作者对我们细化 2D-IR 传输光谱以去除来自腔中非极化激元分子的背景贡献的方法提出了异议。在对他们的评论的回应中,我们描述了我们的方法是如何受到作者之前工作的启发的,并且我们提出了一个具有空间依赖性的分子-腔 Tavis-Cummings 模型,该模型可以解释具有非零振子强度的局域分子的显著响应。局域分子响应的明显特征是在极性的乙酸丁酯溶剂中,W(CO)分子的裸态的光谱扩散动力学。由于将大量分子耦合到腔模时的交换窄化程度极高,因此在极化激元态中不存在非均匀展宽。

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