Polariton induced conical intersection and berry phase
Polariton induced conical intersection and berry phase
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DOI：
10.1039/d1cp00943e
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发表时间：
2021-07-19
影响因子：
3.3
通讯作者：
Huo, Pengfei
中科院分区：
文献类型：
--
作者：
Farag, Marwa H.;Mandal, Arkajit;Huo, Pengfei
本文研究了双原子分子在光学腔内与量子化光子模式耦合所产生的极化激子诱导圆锥交叉（PICI），以及相应的Berry相位效应。我们使用严格的Pauli-Fierz哈密顿量来描述LiF分子与腔之间的量子光-物质相互作用，并使用精确的量子传播来研究极化子量子动力学。相对于腔偏振方向的分子旋转作为PICI的调谐模式，即使在双原子分子内也能产生有效的CI。为了清楚地展示Berry相的动力学效应，我们构建了两个具有相同Born-Oppenheimer表面的附加模型，但去除了几何相位的影响。我们发现，当初始波函数位于较低极化表面时，从核概率分布可以看出，Berry相位在绕CI后引起波函数的pi相移。另一方面，当初始波函数放置在极化表面上时，几何相位显著影响极化态之间的耦合，从而影响它们之间的居群动力学。这些BP效应通过光片段的角度分布得到了进一步的证明。由量子化辐射场产生的PICI有望为调节光化学反应开辟新的可能性。
We investigate the Polariton induced conical intersection (PICI) created from coupling a diatomic molecule with the quantized photon mode inside an optical cavity, and the corresponding Berry Phase effects. We use the rigorous Pauli-Fierz Hamiltonian to describe the quantum light-matter interactions between a LiF molecule and the cavity, and use the exact quantum propagation to investigate the polariton quantum dynamics. The molecular rotations relative to the cavity polarization direction play a role as the tuning mode of the PICI, resulting in an effective CI even within a diatomic molecule. To clearly demonstrate the dynamical effects of the Berry phase, we construct two additional models that have the same Born-Oppenheimer surface, but the effects of the geometric phase are removed. We find that when the initial wavefunction is placed in the lower polaritonic surface, the Berry phase causes a pi phase-shift in the wavefunction after the encirclement around the CI, indicated from the nuclear probability distribution. On the other hand, when the initial wavefunction is placed in the upper polaritonic surface, the geometric phase significantly influences the couplings between polaritonic states and therefore, the population dynamics between them. These BP effects are further demonstrated through the photo-fragment angular distribution. PICI created from the quantized radiation field has the promise to open up new possibilities to modulate photochemical reactivities.