We demonstrate that collective vibrational strong coupling of molecules in thermal equilibrium can give rise to significant local electronic polarizations in the thermodynamic limit. We do so by first showing that the full nonrelativistic Pauli–Fierz problem of an ensemble of strongly coupled molecules in the dilute-gas limit reduces in the cavity Born–Oppenheimer approximation to a cavity–Hartree equation for the electronic structure. Consequently, each individual molecule experiences a self-consistent coupling to the dipoles of all other molecules, which amount to non-negligible values in the thermodynamic limit (large ensembles). Thus, collective vibrational strong coupling can alter individual molecules strongly for localized ”hotspots” within the ensemble. Moreover, the discovered cavity-induced polarization pattern possesses a zero net polarization, which resembles a continuous form of a spin glass (or better polarization glass). Our findings suggest that the thorough understanding of polaritonic chemistry, requires a self-consistent treatment of dressed electronic structure, which can give rise to numerous, so far overlooked, physical mechanisms.

中文翻译：

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从集体振动强耦合中揭示空腔诱导分子极化机制

我们证明，热平衡中分子的集体振动强耦合可以在热力学极限内引起显着的局部电子极化。为此，我们首先证明了稀气体极限下强耦合分子系综的完全非相对论泡利-菲尔兹问题在电子结构的空腔玻恩-奥本海默近似中简化为空腔-哈特里方程。因此，每个单独的分子都会经历与所有其他分子的偶极子的自洽耦合，这相当于热力学极限（大系综）中不可忽略的值。因此，集体振动强耦合可以强烈改变单个分子，以形成整体中的局部“热点”。此外，所发现的腔致偏振图案具有零净偏振，类似于旋转玻璃（或更好的偏振玻璃）的连续形式。我们的研究结果表明，对极化子化学的彻底理解需要对修饰的电子结构进行自洽的处理，这可能会产生许多迄今为止被忽视的物理机制。