統一福斯特以及修正瑞德菲爾動力學的新理論: 純相移變分極化子參考系統量子主方程

Abstract

激發能量轉移在光合作用系統中發揮關鍵作用。這個過程的效率和根本重要性使激發能量轉移研究成為科學探究的一個重要領域。激發能量轉移動力學建模的傳統方法，例如用於非相干能量轉移的福斯特理論(FT) 和用於相干轉移的修正雷德菲爾德理論 (CMRT)，在各種系統中都面臨著限制。本研究引入了一個統一的量子主方程式框架，稱為純相移變分極化子參考系統量子主方程式（PDVPRS-QME），它融合了FT和CMRT的特點，彌補了這些傳統範式之間的差距。 PDVPRS-QME考慮了獨特的交叉項，這對於準確捕捉中間狀態的動態至關重要，同時提供跨不同系統浴耦合強度的更廣泛的適用性。透過針對準絕熱傳播器路徑積分結果的數值基準以及與FT和CMRT的比較，PDVPRS-QME被證明可以透過確定最佳參考系統來改進傳統的微擾方法。這項研究強調了選擇適當基礎的重要性，並為推導量子主方程式提供了新的視角。

Excitation energy transfer (EET) plays a pivotal role within photosynthetic systems. The efficiency and fundamental importance of this process elevate the study of EET as a vital area of scientific inquiry. Traditional methodologies for modeling EET dynamics, such as Förster Theory (FT) for incoherent energy transfer and the modified Redfield Theory (mRT) for coherent transfer, face limitations across various parameter regimes. This study introduces a unified quantum master equation framework, referred to as pure dephasing variational polaron reference system quantum master equation (PDVPRS-QME), which melds the characteristics of both FT and CMRT to bridge the gap between these traditional paradigms. The PDVPRS-QME accounts for unique cross-terms essential for accurately capturing the dynamics in intermediate system-bath coupling regimes alongside providing broader applicability across a broad range of system-bath coupling strengths. Through numerical benchmarks against quasiadiabatic propagator path integral (QUAPI) results and comparison with FT and CMRT, PDVPRS-QME is demonstrated to improve upon conventional perturbative approaches by determining an optimal reference system. This study underscores the significance of selecting an appropriate basis and provides a novel perspective for deriving QME.