Reply to “Comment on: ‘Isolating Vibrational Polariton 2D-IR Transmission Spectra’”
Reply to “Comment on: ‘Isolating Vibrational Polariton 2D-IR Transmission Spectra’”
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回复 — 评论： — 隔离振动极化子 2D-IR 透射光谱 — —
DOI：
10.1021/acs.jpclett.2c02823
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Kubarych, Kevin J.
中科院分区：
文献类型：
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作者：
Duan, Rong;Mastron, Joseph N.;Song, Yin;Kubarych, Kevin J.
在对我们最近的一封信的评论中，作者对我们改进2D-IR透射光谱的方法提出了异议，该方法消除了腔中非极化激元分子产生的背景贡献。在我们对他们的评论的回应中，我们描述了我们的方法是如何被作者以前的工作所激励的，并且我们提出了一个空间依赖的分子腔Tavis-Cummings模型，该模型可以解释具有非零振子强度的局部分子的显着响应。局部化分子响应的标志是裸露的W（CO）6分子在极性乙酸丁酯溶剂中的光谱扩散动力学。由于在将非常大量的分子耦合到腔模时交换变窄的极端程度，极化激元态不存在不均匀的加宽。
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)6molecules 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.