Fredin Lisa A, Persson Petter
Chemical Informatics Research Group, Chemical Sciences Division, Material Measurement Laboratory, National Institute of Standards and Technology, 100 Bureau Drive, Mailstop 8320, Gaithersburg, Maryland 20899, USA.
Chemistry Department, Theoretical Chemistry Division, Lund University, Box 124, SE-22100 Lund, Sweden.
J Chem Phys. 2016 Sep 14;145(10):104310. doi: 10.1063/1.4962254.
The rapidly growing interest in photocatalytic systems for direct solar fuel production such as hydrogen generation from water splitting is grounded in the unique opportunity to achieve charge separation in molecular systems provided by electron transfer processes. In general, both photoinduced and catalytic processes involve complicated dynamics that depend on both structural and electronic effects. Here the excited state landscape of metal centered light harvester-catalyst pairs is explored using density functional theory calculations. In weakly bound systems, the interplay between structural and electronic factors involved can be constructed from the various mononuclear relaxed excited states. For this study, supramolecular states of electron transfer and excitation energy transfer character have been constructed from constituent full optimizations of multiple charge/spin states for a set of three Ru-based light harvesters and nine transition metal catalysts (based on Ru, Rh, Re, Pd, and Co) in terms of energy, structure, and electronic properties. The complete set of combined charge-spin states for each donor-acceptor system provides information about the competition of excited state energy transfer states with the catalytically active electron transfer states, enabling the identification of the most promising candidates for photocatalytic applications from this perspective.
对用于直接太阳能燃料生产的光催化系统（如通过水分解制氢）的兴趣迅速增长，其基础在于电子转移过程为分子系统提供了实现电荷分离的独特机会。一般来说，光诱导过程和催化过程都涉及复杂的动力学，这取决于结构和电子效应。本文利用密度泛函理论计算探索了以金属为中心的光捕获剂-催化剂对的激发态态势。在弱束缚体系中，所涉及的结构和电子因素之间的相互作用可以从各种单核弛豫激发态构建。对于本研究，已根据能量、结构和电子性质，通过对一组三种钌基光捕获剂和九种过渡金属催化剂（基于钌、铑、铼、钯和钴）的多个电荷/自旋态进行完整优化，构建了具有电子转移和激发能量转移特征的超分子态。每个供体-受体系统的完整电荷-自旋态组合集提供了有关激发态能量转移态与催化活性电子转移态竞争的信息，从而能够从这一角度识别出最有前景的光催化应用候选物。
