The non-Markovianity of the electron transfer in an oligothiophene-fullerene heterojunction described by a spin-boson model is analyzed using the time dependent decoherence canonical rates and the volume of accessible states in the Bloch sphere. The dynamical map of the reduced electronic system is computed by the hierarchical equations of motion methodology (HEOM) providing an exact dynamics. Transitory witness of non-Markovianity is linked to the bath dynamics analyzed from the HEOM auxiliary matrices. The signature of the collective bath mode detected from HEOM in each electronic state is compared with predictions of the effective mode extracted from the spectral density. We show that including this main reaction coordinate in a one-dimensional vibronic system coupled to a residual bath satisfactorily describes the electron transfer by a simple Markovian Redfield equation. Non-Markovianity is computed for three inter fragment distances and compared with a priori criterion based on the system and bath characteristic timescales.

使用与时间相关的退相干经典率和布洛赫球中可及态的体积，分析了自旋玻色子模型描述的低聚噻吩-富勒烯异质结中电子转移的非马尔可夫性。简化的电子系统的动力学图是通过运动方法的分层方程式（HEOM）计算得出的，该方法具有精确的动力学特性。非马尔可夫性的暂时见证与从HEOM辅助矩阵分析的熔池动力学有关。将在每种电子状态下从HEOM中检测到的集体浴池模式的特征与从光谱密度中提取的有效模式的预测进行比较。我们表明，在与残余浴耦合的一维振动系统中包括该主要反应坐标，可以通过简单的马尔可夫Redfield方程令人满意地描述电子转移。计算三个片段间距离的非马尔可夫性，并与基于系统和浴槽特征时标的先验标准。