Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
J Phys Chem Lett. 2022 Mar 17;13(10):2330-2337. doi: 10.1021/acs.jpclett.2c00122. Epub 2022 Mar 4.
We show that combining the linearized semiclasscial approximation with Fermi's golden rule (FGR) rate theory gives rise to a general-purpose cost-effective and scalable computational framework that can accurately capture the cavity-induced rate enhancement of charge transfer reactions that occurs when the molecular system is placed inside a microcavity. Both partial linearization with respect to the nuclear and photonic degrees of freedom and full linerization with respect to nuclear, photonic, and electronic degrees of freedom (the latter within the mapping Hamiltonian approach) are shown to be highly accurate, provided that the Wigner transforms of the product (WoP) of operators at the initial time is not replaced by the product of their Wigner transforms. We also show that the partial linearization method yields the quantum-mechanically exact cavity-modified FGR rate constant for a model system in which the donor and acceptor potential energy surfaces are harmonic and identical except for a shift in the equilibrium energy and geometry, if WoP is applied.
我们表明，将线性化半经典逼近与费米的黄金规则（FGR）速率理论相结合，会产生一种通用的、具有成本效益且可扩展的计算框架，该框架可以准确捕捉到分子系统置于微腔中时发生的电荷转移反应的腔诱导速率增强。相对于核和光子自由度的部分线性化以及相对于核、光子和电子自由度的完全线性化（在后一种情况下，在映射哈密顿量方法内）都被证明是高度准确的，前提是初始时刻算子的乘积（WoP）的维格纳变换不被其维格纳变换的乘积替换。我们还表明，如果应用 WoP，对于除平衡能量和几何形状发生位移之外的势能表面是谐波且相同的施主和受主模型系统，部分线性化方法会产生量子力学上精确的腔修正 FGR 速率常数。
