Schnappinger Thomas, Sidler Dominik, Ruggenthaler Michael, Rubio Angel, Kowalewski Markus
Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm, Sweden.
Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science, Luruper Chaussee 149, 22761 Hamburg, Germany.
J Phys Chem Lett. 2023 Sep 14;14(36):8024-8033. doi: 10.1021/acs.jpclett.3c01842. Epub 2023 Aug 31.
Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, the current understanding of the interplay between molecules and confined light modes is incomplete. Accurate theoretical models that take into account intermolecular interactions to describe ensembles are therefore essential to understand the mechanisms governing polaritonic chemistry. We present an Hartree-Fock ansatz in the framework of the cavity Born-Oppenheimer approximation and study molecules strongly interacting with an optical cavity. This ansatz provides a nonperturbative, self-consistent description of strongly coupled molecular ensembles, taking into account the cavity-mediated dipole self-energy contributions. To demonstrate the capability of the cavity Born-Oppenheimer Hartree-Fock ansatz, we study the collective effects in ensembles of strongly coupled diatomic hydrogen fluoride molecules. Our results highlight the importance of the cavity-mediated intermolecular dipole-dipole interactions, which lead to energetic changes of individual molecules in the coupled ensemble.
实验研究表明，光学腔可以通过振动或电子强耦合以及量子化的腔模来影响化学反应。然而，目前对分子与受限光模之间相互作用的理解并不完整。因此，考虑分子间相互作用以描述系综的精确理论模型对于理解极化子化学的调控机制至关重要。我们在腔玻恩-奥本海默近似框架下提出了一种哈特里-福克近似，并研究了与光学腔强烈相互作用的分子。这种近似考虑了腔介导的偶极自能贡献，提供了一种非微扰、自洽的强耦合分子系综描述。为了证明腔玻恩-奥本海默哈特里-福克近似的能力，我们研究了强耦合双原子氟化氢分子系综中的集体效应。我们的结果突出了腔介导的分子间偶极-偶极相互作用的重要性，这种相互作用导致了耦合系综中单个分子的能量变化。
