论文标题
从量子量子电动力学中了解极化化学
Understanding polaritonic chemistry from ab initio quantum electrodynamics
论文作者
论文摘要
在这篇综述中,我们介绍了理论基础和第一原理框架,以描述低能量制度中量子电动力学(QED)中的量子问题。具有对相互作用的光子,电子和核/离子的严格且完全量化的描述,从弱到强的光耦合方案,对于对极化化学和空腔材料工程的新兴领域的详细理解是至关重要的。严格的第一原理的使用避免了基于光,物质及其相互作用的现象学描述使用近似模型所引起的歧义和问题。通过从基本的物理和数学原理开始,我们首先详细综述了非相关的QED,该QED可以通过求解Schrödinger-type方程来非扰动地研究极性系统。由此产生的Pauli-Fierz量子场理论是计算方法开发的基石,例如量子 - 电动力学密度功能理论,QED耦合群集或腔体born-Opphemer Molecular Molecular分子动力学。这些方法在相等的基础上处理光和物质,并且具有与既定的计算化学和电子结构理论的精度和可靠性相同的水平。在概述了这些新颖的QED方法背后的钥匙界之后,我们解释了它们的好处,以更好地理解光子诱导的化学性质和反应变化。基于从头算法获得的结果,我们确定了开放的理论问题,以及如何建立对极化化学的机械理解。最终,我们对北极星化学和第一原则的未来方向进行展望,并解决了未来几年需要从理论和实验观点上解决的开放问题。
In this review we present the theoretical foundations and first principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime. Having a rigorous and fully quantized description of interacting photons, electrons and nuclei/ions, from weak to strong light-matter coupling regimes, is pivotal for a detailed understanding of the emerging fields of polaritonic chemistry and cavity materials engineering. The use of rigorous first principles avoids ambiguities and problems stemming from using approximate models based on phenomenological descriptions of light, matter and their interactions. By starting from fundamental physical and mathematical principles, we first review in great detail non-relativistic QED, which allows to study polaritonic systems non-perturbatively by solving a Schrödinger-type equation. The resulting Pauli-Fierz quantum field theory serves as a cornerstone for the development of computational methods, such as quantum-electrodynamical density functional theory, QED coupled cluster or cavity Born-Oppenheimer molecular dynamics. These methods treat light and matter on equal footing and have the same level of accuracy and reliability as established methods of computational chemistry and electronic structure theory. After an overview of the key-ideas behind those novel ab initio QED methods, we explain their benefits for a better understanding of photon-induced changes of chemical properties and reactions. Based on results obtained by ab initio QED methods we identify the open theoretical questions and how a so far missing mechanistic understanding of polaritonic chemistry can be established. We finally give an outlook on future directions within polaritonic chemistry and first principles QED and address the open questions that need to be solved in the next years both from a theoretical as well as experimental viewpoint.