Davidsson Eric, Kowalewski Markus
Department of Physics, Stockholm University, Albanova University Centre, SE-106 91 Stockholm, Sweden.
J Phys Chem A. 2020 Jun 11;124(23):4672-4677. doi: 10.1021/acs.jpca.0c03867. Epub 2020 May 29.
Strong light-matter coupling can modify the photochemistry of molecular systems. The collective dynamics of an ensemble of molecules coupled to the light field plays a crucial role in experimental observations. However, the theory of polaritonic chemistry is primarily understood in terms of single molecules, since even in small molecular ensembles the collective dynamics becomes difficult to disentangle. Understanding of the underlying ensemble mechanisms is key to a conceptual understanding and interpretation of experiments. We present a model system that simplifies the problem by mixing two-level Mg atoms with a single MgH molecule and investigate its collective dynamics. Our focus is on the modified chemical properties of a single diatomic molecule in the presence of an ensemble of resonant atoms as well as the structure of the major and intermediate polariton states. We present quantum dynamics simulations of the coupled vibronic-photonic system for a variable size of the atomic ensemble. Special attention is given to dissociative the dynamics of the MgH molecule.
强光与物质耦合能够改变分子体系的光化学性质。与光场耦合的分子系综的集体动力学在实验观测中起着至关重要的作用。然而，极化子化学理论主要是基于单分子来理解的，因为即使在小分子系综中，集体动力学也变得难以厘清。理解潜在的系综机制是从概念上理解和解释实验的关键。我们提出了一个模型系统，通过将二能级Mg原子与单个MgH分子混合来简化问题，并研究其集体动力学。我们关注的是在共振原子系综存在的情况下单个双原子分子的化学性质变化以及主要和中间极化子态的结构。我们给出了针对不同大小原子系综的耦合振子 - 光子系统的量子动力学模拟。特别关注了MgH分子的解离动力学。
