Theory for Nonlinear Spectroscopy of Vibrational Polaritons
Theory for Nonlinear Spectroscopy of Vibrational Polaritons
复制标题
DOI：
10.1021/acs.jpclett.8b01176
复制
发表时间：
2018-07-05
影响因子：
5.7
通讯作者：
Yuen-Zhou, Joel
中科院分区：
文献类型：
--
作者：
Ribeiro, Raphael F.;Dunkelberger, Adam D.;Yuen-Zhou, Joel
分子极化子由于其利用电磁相干来控制纳米级分子过程的潜力而得到了相当大的关注。尽管最近对液体振动极化子的实验显示了利用这些效应的巨大希望，但在解释它们的光谱特征方面仍然存在重大挑战。基于量子朗之万方程和输入-输出理论，我们建立了这类极化子的泵浦-探测光谱的量子力学理论。与最近的实验数据比较表明，考虑到调制信号的各种振动非谐性，这一结果符合得很好。最后，基于有效的模式耦合理论，对数据进行了简单直观的解释。我们的工作为阐明分子极化子的非线性光学性质以及进一步分析这些系统的多维光谱实验提供了坚实的理论框架。
Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. We develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum Langevin equation and the input-output theory. Comparison with recent experimental data shows good agreement upon consideration of the various vibrational anharmonicities that modulate the signals. Finally, a simple and intuitive interpretation of the data based on an effective mode-coupling theory is provided. Our work provides a solid theoretical framework to elucidate nonlinear optical properties of molecular polaritons as well as to analyze further multidimensional spectroscopy experiments on these systems.