Antoniou Panayiota, Suchanek Figen, Varner James F, Foley Jonathan J
Department of Chemistry, William Paterson University, 300 Pompton Road, Wayne, New Jersey 07470, United States.
J Phys Chem Lett. 2020 Nov 5;11(21):9063-9069. doi: 10.1021/acs.jpclett.0c02406. Epub 2020 Oct 12.
We present a non-Hermitian formulation of the polaritonic structure of azobenzene strongly coupled to a photonic mode that explicitly accounts for the fleeting nature of the photon-molecule interaction. This formalism reveals that the polaritonic nonadiabatic couplings that facilitate cis-trans isomerization can be dramatically modified by photonic dissipation. We perform Fewest-Switches Surface Hopping dynamics on the surfaces that derive from our non-Hermitian formalism and find that the polaritonic isomerization yields are strongly suppressed for moderate dissipation rates and that cavity-free isomerization dynamics are recovered under large dissipation rates. These findings highlight the important role that the finite lifetime of photonic degrees of freedom play in polaritonic chemistry.
我们提出了一种非厄米形式的偶氮苯极化激元结构，该结构与光子模式强耦合，明确考虑了光子 - 分子相互作用的短暂性质。这种形式体系表明，促进顺反异构化的极化激元非绝热耦合会因光子耗散而发生显著改变。我们在源自非厄米形式体系的表面上进行最少开关表面跳跃动力学计算，发现对于中等耗散率，极化激元异构化产率会受到强烈抑制，而在大耗散率下则恢复无腔异构化动力学。这些发现突出了光子自由度的有限寿命在极化激元化学中所起的重要作用。
