Mondal Monosij, Semenov Alexander, Ochoa Maicol A, Nitzan Abraham
Department of Chemistry, University of Pennsylvania, PhiladelphiaPennsylvania19104, United States.
School of Chemistry, Tel Aviv University, Tel Aviv69978, Israel.
J Phys Chem Lett. 2022 Oct 20;13(41):9673-9678. doi: 10.1021/acs.jpclett.2c02304. Epub 2022 Oct 10.
Controlling molecular spectroscopy and even chemical behavior in a cavity environment is a subject of intense experimental and theoretical interest. In Fabry-Pérot cavities, strong (radiation-matter) coupling phenomena without an intense radiation field often rely on the number of chromophore molecules collectively interacting with a cavity mode. For plasmonic cavities, the cavity field-matter coupling can be strong enough to manifest strong coupling involving even a single molecule. To this end, infrared plasmonic cavities can be particularly useful in understanding vibrational strong coupling. Here we present a procedure for estimating the radiation-matter coupling and, equivalently, the mode volume as well as the mode lifetime and quality factor for plasmonic cavities of arbitrary shapes and use it to estimate these quantities for infrared cavities of two particularly relevant geometries comprising several n-doped semiconductors. Our calculations demonstrate very high field confinement and low mode volumes of these cavities despite having relatively low quality factors, which is often the case for plasmonic cavities.
在腔环境中控制分子光谱甚至化学行为是一个受到强烈实验和理论关注的课题。在法布里 - 珀罗腔中,没有强辐射场时的强(辐射 - 物质)耦合现象通常依赖于发色团分子集体与腔模相互作用的数量。对于等离子体腔,腔场与物质的耦合可以足够强,以至于即使涉及单个分子也能表现出强耦合。为此,红外等离子体腔在理解振动强耦合方面可能特别有用。在这里,我们提出了一种用于估计任意形状等离子体腔的辐射 - 物质耦合、等效的模体积以及模寿命和品质因数的方法,并将其用于估计由几种n型掺杂半导体组成的两种特别相关几何形状的红外腔的这些量。我们的计算表明,尽管这些腔的品质因数相对较低,但它们具有非常高的场限制和低模体积,这在等离子体腔中是常见的情况。