Solvated dielectrons from optical excitation: An effective source of low-energy electrons
Solvated dielectrons from optical excitation: An effective source of low-energy electrons
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DOI：
10.1126/science.adh0184
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发表时间：
2023-06-16
期刊：
影响因子：
56.9
通讯作者：
Signorell, Ruth
中科院分区：
文献类型：
--
作者：
Hartweg, Sebastian;Barnes, Jonathan;Signorell, Ruth
溶解在液氨或水介质中的低能电子是强大的还原剂，可促进具有挑战性的还原反应，但也可能对生物组织造成辐射损伤。关于潜在的机械过程的知识仍然不完整，特别是关于电子转移步骤的细节和能量学。在这项工作中，我们展示了金属-氨簇的紫外（UV）光激发如何用于原位产生可调谐的低能电子。具体来说，我们确定了紫外光诱导的自旋配对溶剂化二电子的产生及其随后通过非常规电子转移介导的衰变作为有效的低能量电子源的弛豫。这一过程是稳定的、直接的，具有提高我们对辐射损伤的理解和促进溶剂化电子还原反应机理研究的前景。
Low-energy electrons dissolved in liquid ammonia or aqueous media are powerful reducing agents that promote challenging reduction reactions but can also cause radiation damage to biological tissue. Knowledge of the underlying mechanistic processes remains incomplete, particularly with respect to the details and energetics of the electron transfer steps. In this work, we show how ultraviolet (UV) photoexcitation of metal-ammonia clusters could be used to generate tunable low-energy electrons in situ. Specifically, we identified UV light-induced generation of spin-paired solvated dielectrons and their subsequent relaxation by an unconventional electron transfer-mediated decay as an efficient, low-energy electron source. The process is robust and straightforward to induce with the prospect of improving our understanding of radiation damage and fostering mechanistic studies of solvated electron reduction reactions.