Chowdhury Sutirtha N, Mandal Arkajit, Huo Pengfei
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14627, USA.
J Chem Phys. 2021 Jan 28;154(4):044109. doi: 10.1063/5.0038330.
We use the ring polymer (RP) representation to quantize the radiation field inside an optical cavity to investigate polariton quantum dynamics. Using a charge transfer model coupled to an optical cavity, we demonstrate that the RP quantization of the photon field provides accurate rate constants of the polariton mediated electron transfer reaction compared to Fermi's golden rule. Because RP quantization uses extended phase space to describe the photon field, it significantly reduces the computational costs compared to the commonly used Fock state description of the radiation field. Compared to the other quasi-classical descriptions of the photon field, such as the classical Wigner based mean-field Ehrenfest model, the RP representation provides a much more accurate description of the polaritonic quantum dynamics because it alleviates the potential quantum distribution leakage problem associated with the photonic degrees of freedom (DOF). This work demonstrates the possibility of using the ring polymer description to treat the quantized radiation field in polariton chemistry, offering an accurate and efficient approach for future investigations in cavity quantum electrodynamics.
我们使用环形聚合物（RP）表示来对光学腔内的辐射场进行量子化，以研究极化激元量子动力学。通过耦合到光学腔的电荷转移模型，我们证明，与费米黄金规则相比，光子场的RP量子化提供了极化激元介导的电子转移反应的精确速率常数。由于RP量子化使用扩展相空间来描述光子场，与常用的辐射场福克态描述相比，它显著降低了计算成本。与光子场的其他准经典描述（如基于经典维格纳的平均场埃伦费斯特模型）相比，RP表示提供了对极化激元量子动力学更准确的描述，因为它缓解了与光子自由度（DOF）相关的潜在量子分布泄漏问题。这项工作证明了使用环形聚合物描述来处理极化激元化学中的量子化辐射场的可能性，为未来腔量子电动力学的研究提供了一种准确而有效的方法。
