Koessler Eric R, Mandal Arkajit, Musser Andrew J, Krauss Todd D, Huo Pengfei
Department of Chemistry, University of Rochester 120 Trustee Road Rochester NY 14627 USA
Department of Chemistry, Texas A&M University College Station TX 77842 USA.
Chem Sci. 2025 May 19;16(25):11644-11658. doi: 10.1039/d5sc01911g. eCollection 2025 Jun 25.
We investigate polariton-mediated electron transfer (PMET) under the collective molecule-cavity coupling regime, with the presence of dark state transfer, cavity loss, and continuous-wave (CW) laser driving using quantum dynamics simulations and analytic rate constant theories. We demonstrate how the PMET rate constant can be enhanced by the collective coupling effect, where the light-matter coupling strength is small, yet there are many molecules collectively coupled to the cavity. We first show how reactions initialized in the collective upper polariton (UP) state can significantly enhance the PMET rate constant by decreasing the reaction driving force of an otherwise uphill ET reaction with collective strong coupling and positive detuning. We further show how the PMET rate constant is affected by dark states and cavity loss, which are often regarded as obstacles, and how to overcome them to provide a significant cavity-induced rate constant enhancement under the collective coupling regime. In particular, we show that by driving the UP state with a CW laser in a positively detuned cavity, the effective PMET rate constant can be several orders of magnitude larger than outside the cavity, even with significant molecular disorder and cavity loss. These results reveal a promising approach to realize photochemical rate enhancement with collective strong coupling in disordered and lossy polariton systems, as well as enabling otherwise impractical uphill ET reactions.
我们利用量子动力学模拟和解析速率常数理论，研究了在集体分子 - 腔耦合机制下，存在暗态转移、腔损耗和连续波（CW）激光驱动时的极化激元介导的电子转移（PMET）。我们展示了在光 - 物质耦合强度较小但有许多分子集体耦合到腔的情况下，集体耦合效应如何提高PMET速率常数。我们首先展示了在集体上极化激元（UP）态中初始化的反应如何通过降低原本具有集体强耦合和正失谐的上坡电子转移反应的反应驱动力，显著提高PMET速率常数。我们进一步展示了PMET速率常数如何受到通常被视为障碍的暗态和腔损耗的影响，以及如何克服它们以在集体耦合机制下实现显著的腔诱导速率常数增强。特别是，我们表明，在正失谐腔中用连续波激光驱动UP态时，即使存在显著的分子无序和腔损耗，有效PMET速率常数也可比腔外大几个数量级。这些结果揭示了一种在无序和有损极化激元系统中通过集体强耦合实现光化学速率增强的有前景的方法，以及实现原本不切实际的上坡电子转移反应的方法。
