Theory of molecular emission power spectra. I. Macroscopic quantum electrodynamics formalism.
Theory of molecular emission power spectra. I. Macroscopic quantum electrodynamics formalism.
复制标题
分子发射功率谱理论。
DOI：
10.1063/5.0027796
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Liang
中科院分区：
文献类型：
--
作者：
Siwei Wang;Ming;Yi;G. Scholes;Liang
我们在宏观量子电动力学框架下研究具有多种振动模式的分子发射器的发射功率谱。我们提出的理论对于任意不均匀、色散和吸收介质存在下的分子自发发射光谱是通用的。此外，理论表明分子发射功率谱可以分解为电磁环境因子和线形函数。为了证明该理论的有效性，我们研究了两个极限下的线形函数。在非相干极限（真空中的单个分子）下，线形函数完全符合弗兰克-康登原理。在相干极限（单个分子与单个极化子或光子强耦合）和高振动频率的条件下，线形函数表现出拉比分裂，其间距与我们之前的理论估计的激子-光子耦合的大小完全相同[S. Wang 等人，J. Chem。物理。 151, 014105 (2019)]。最后，我们探讨了激子-光子和电子-声子相互作用对空腔中单个分子线形函数的影响。理论表明，线形函数的电子振动结构并不总是随着激子-光子耦合的增加而消失，这与介电环境的损失有关。
We study the emission power spectrum of a molecular emitter with multiple vibrational modes in the framework of macroscopic quantum electrodynamics. The theory we present is general for a molecular spontaneous emission spectrum in the presence of arbitrary inhomogeneous, dispersive, and absorbing media. Moreover, the theory shows that the molecular emission power spectra can be decomposed into the electromagnetic environment factor and lineshape function. In order to demonstrate the validity of the theory, we investigate the lineshape function in two limits. In the incoherent limit (single molecules in a vacuum), the lineshape function exactly corresponds to the Franck-Condon principle. In the coherent limit (single molecules strongly coupled with single polaritons or photons) together with the condition of high vibrational frequency, the lineshape function exhibits a Rabi splitting, the spacing of which is exactly the same as the magnitude of exciton-photon coupling estimated by our previous theory [S. Wang et al., J. Chem. Phys. 151, 014105 (2019)]. Finally, we explore the influence of exciton-photon and electron-phonon interactions on the lineshape function of a single molecule in a cavity. The theory shows that the vibronic structure of the lineshape function does not always disappear as the exciton-photon coupling increases, and it is related to the loss of a dielectric environment.
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DOI：
10.1146/annurev.anchem.1.031207.112814
发表时间：
2008-01-01
影响因子：
8
作者：
Stiles, Paul. L.;Dieringer, Jon A.;Van Duyne, Richard R.
通讯作者：
Van Duyne, Richard R.
影响因子：
56.9
作者：
Xiang, Bo;Ribeiro, Raphael F.;Xiong, Wei
通讯作者：
Xiong, Wei
影响因子：
3.7
作者：
Ding, Wendu;Hsu, Liang-Yan;Schatz, George C.
通讯作者：
Schatz, George C.
影响因子：
16.6
作者：
通讯作者：
--
影响因子：
16.6
作者：
Campos-Gonzalez-Angulo, Jorge A.;Ribeiro, Raphael F.;Yuen-Zhou, Joel
通讯作者：
Yuen-Zhou, Joel