This work explores the concept that differential wave function overlap between excited states can be engineered within a molecular chromophore. The aim is to control excited state wave function symmetries, so that symmetry matches or mismatches result in differential orbital overlap and define low-energy trajectories or kinetic barriers within the excited state surface, that drive excited state population toward different reaction pathways. Two donor–acceptor assemblies were explored, where visible light absorption prepares excited states of different wave function symmetry. These states could be resolved using transient absorption spectroscopy, thanks to wave function symmetry-specific photoinduced optical transitions. One of these excited states undergoes energy transfer to the acceptor, while another undertakes a back-electron transfer to restate the ground state. This differential behavior is possible thanks to the presence of kinetic barriers that prevent excited state equilibration. This strategy can be exploited to avoid energy dissipation in energy conversion or photoredox catalytic schemes.

这项工作探索了激发态之间的微分波函数重叠可以在分子发色团内设计的概念。目的是控制激发态波函数的对称性，使对称性匹配或不匹配导致不同的轨道重叠，并在激发态表面内定义低能轨迹或动力学势垒，从而将激发态群体推向不同的反应途径。探索了两种供体-受体组件，其中可见光吸收准备了不同波函数对称性的激发态。由于波函数对称特定的光诱导光学跃迁，这些状态可以使用瞬态吸收光谱来解决。这些激发态之一经历能量转移到受体，而另一个进行反向电子转移以重述基态。由于存在阻止激发态平衡的动力学障碍，这种差异行为是可能的。该策略可用于避免能量转换或光氧化还原催化方案中的能量耗散。