Although Marcus theory is widely used to describe charge transfer in molecular systems, in its usual form it is restricted to transfer from one molecule to another. If a charge is delocalised across multiple donor molecules, this approach requires us to treat the entire donor aggregate as a unified supermolecule, leading to potentially expensive quantum-chemical calculations and making it more difficult to understand how the aggregate components contribute to the overall transfer. Here, we show that it is possible to describe charge transfer between groups of molecules in terms of the properties of the constituent molecules and couplings between them, obviating the need for expensive supermolecular calculations. We use the resulting theory to show that charge delocalisation between molecules in either the donor or acceptor aggregates can enhance the rate of charge transfer through a process we call supertransfer (or suppress it through subtransfer). The rate can also be enhanced above what is possible with a single donor and a single acceptor by judiciously tuning energy levels and reorganisation energies. We also describe bridge-mediated charge transfer between delocalised molecular aggregates. The equations of generalised Marcus theory are in closed form, providing qualitative insight into the impact of delocalisation on charge dynamics in molecular systems.

中文翻译：

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广义马库斯理论用于多分子离域电荷转移

尽管马库斯理论被广泛用于描述分子系统中的电荷转移，但以其通常的形式它被限制从一个分子转移到另一个分子。如果电荷跨多个供体分子分散，这种方法要求我们将整个供体聚集体视为一个统一的超分子，从而导致潜在的昂贵的量子化学计算，并使人们更加难以理解聚集体组分如何促进整体转移。在这里，我们表明可以根据组成分子的性质和它们之间的偶联来描述分子组之间的电荷转移，从而无需进行昂贵的超分子计算。我们使用得出的理论来表明，供体或受体聚集体中分子之间的电荷离域化可以通过我们称为超转移的过程（或通过亚转移抑制）来提高电荷转移的速率。通过明智地调整能级和重组能，该速率也可以提高到单个供体和单个受体所能达到的水平以上。我们还描述了离域分子聚集体之间的桥梁介导的电荷转移。广义马库斯理论的方程式为封闭形式，可提供定性洞察力，了解离域对分子系统中电荷动力学的影响。通过明智地调整能级和重组能，该速率也可以提高到单个供体和单个受体所能达到的水平以上。我们还描述了离域分子聚集体之间的桥梁介导的电荷转移。广义马库斯理论的方程式为封闭形式，可提供定性洞察力，了解离域对分子系统中电荷动力学的影响。通过明智地调整能级和重组能，该速率也可以提高到单个供体和单个受体所能达到的水平以上。我们还描述了离域分子聚集体之间的桥梁介导的电荷转移。广义马库斯理论的方程式为封闭形式，可提供定性洞察力，了解离域对分子系统中电荷动力学的影响。