Cavity catalysis: using the quantum vacuum to change a chemical reaction

最近，人们对利用空腔限制来改变化学反应的速率或结果的可能性很感兴趣[1,2]。这种情况发生在强耦合状态下，其中宏观数量的分子电子或振动跃迁耦合到谐振腔模式，产生两个亮-物质模式（极化）和一些暗态。值得注意的是，这可以在没有外部光子源的情况下发生，即空腔。该项目的目的是建立在光学腔中发生的化学反应的理论模型，特别是了解强耦合在化学动力学中的作用，并提出可以观察腔催化的实验。这项工作将有助于极性化学的新兴领域，包括在腔内进行化学合成的新方案的潜力。该项目将利用一种新的精确数值技术来模拟圣安德鲁斯大学开发的开放量子系统。该技术允许对与环境强耦合的量子系统进行有效的模拟，并应与分析技术一起用于模拟腔中分子的化学反应动力学，将腔模式和分子振动视为强耦合。参考文献[1]振动极性对热活化化学反应的共振催化Campos-Gonzalez-Angulo等https://arxiv.org/abs/1902.10264[2]通过振动强耦合使基态反应性景观倾斜thomas等。基于时间演化矩阵积算子的高效非马尔可夫量子动力学[j] .科学（英文版）363 615 （2019）《自然通讯》9 3322 （2018）

There has been recent interest in the possibility of using cavity confinement toalter the rate or outcome of a chemical reaction [1,2]. This occurs in theregime of strong coupling where a macroscopic number of molecular electronic orvibrational transitions couple to a resonant cavity mode to produce two brightlight-matter modes (polaritons) and a number of dark states. Noteworthy is thatthis can take place in the absence of external photon source i.e. an emptycavity. The aim of the project is to build theoretical models of chemical reactionsoccurring in an optical cavity, in particular to understand the role of strongcoupling in chemical kinetics and propose experiments in which cavity catalysiscould be observed. This work will contribute to the emerging field of polaritonchemistry including the potential for novel schemes of chemical synthesis takingplace inside a cavity. The project will make use of a new exact numerical technique for modelling openquantum systems developed at St Andrews [3]. This technique allows for efficientsimulation of quantum systems strongly coupled to an environment and shall beused alongside analytical techniques to model chemical reaction dynamics ofmolecules in a cavity, treating the cavity modes and molecular vibrations asstrongly coupled.References[1] Resonant catalysis of thermally-activated chemical reactions with vibrationalpolaritons Campos-Gonzalez-Angulo et al. https://arxiv.org/abs/1902.10264[2] Tilting a ground-state reactivity landscape by vibrational strong couplingThomas et al. Science 363 615 (2019)[3] Efficient non-Markovian quantum dynamics using time-evolving matrix product operatorsStrathearn et al. Nature Comms. 9 3322 (2018)