论文标题
沿有效模式的振动共振介导了兴奋的耦合聚集体中的选择性能量转移
Vibronic Resonance Along Effective Modes Mediates Selective Energy Transfer in Excitonically Coupled Aggregates
论文作者
论文摘要
我们最近提出了兴奋的耦合聚集体的有效正常模式，这些模式沿有效的正常模式准确地将能量转移的哈密顿量转化为一维汉密尔顿人的总和。确定最大程度地促进振动混合的物理有意义的振动动作表明，利用振动 - 电子共振的一种有趣的可能性来介导选择性能量转移。在这里，我们在有效模式方法上扩展了阐明其迭代性质的较大聚集体的迭代性质，并将介导的能量转移的想法扩展到较大的聚集体。我们表明，电子未偶联但静脉共振的供体 - 受体位点之间的能量转移不取决于中间位点的能量或中间位点的数量。中间位点只是介导电子耦合，使得沿特定启动子模式的振动耦合导致直接供体 - 受体能量转移绕过任何中间上坡上坡能量传递步骤。我们表明，电子哈密顿量与有效模式转换之间的相互作用沿特定启动子模式进行线性振动耦合，以决定介导的能量转移的选择性，这在振动耦合和多晶状体基态状态之间的干扰起着至关重要的作用。我们的结果表明，通过振动共振和弱介导的电子耦合的协同效应来增强能量传递的一般设计原理，其中两种效应都不会促进有效的能量传递。此处提出的有效模式方法铺平了一条轻松的途径，朝着较大骨料的四波形光谱模拟，而无需严格近似于谐振振动耦合。
We recently proposed effective normal modes for excitonically coupled aggregates which exactly transform the energy transfer Hamiltonian into a sum of one-dimensional Hamiltonians along the effective normal modes. Identifying physically meaningful vibrational motions which maximally promote vibronic mixing suggested an interesting possibility of leveraging vibrational-electronic resonance for mediating selective energy transfer. Here we expand on the effective mode approach elucidating its iterative nature for successively larger aggregates, and extend the idea of mediated energy transfer to larger aggregates. We show that energy transfer between electronically uncoupled but vibronically resonant donor-acceptor sites does not depend on the intermediate site energy or the number of intermediate sites. The intermediate sites simply mediate electronic coupling such that vibronic coupling along specific promoter modes leads to direct donor-acceptor energy transfer bypassing any intermediate uphill energy transfer steps. We show that interplay between the electronic Hamiltonian and the effective mode transformation partitions the linear vibronic coupling along specific promoter modes to dictate the selectivity of mediated energy transfer, with a vital role of interference between vibronic couplings and multi-particle basis states. Our results suggest a general design principle for enhancing energy transfer through synergistic effects of vibronic resonance and weak mediated electronic coupling, where both effects individually do not promote efficient energy transfer. The effective mode approach proposed here paves a facile route towards four-wavemixing spectroscopy simulations of larger aggregates without severely approximating resonant vibronic coupling.
