Electric Field Effects on Excited State and Electron Transfer Dynamics

在无机、生物无机和有机金属化学专业的这个项目中，将研究外加电场对各种分子的吸收和发射光谱的影响，以及对电子转移反应速率的影响。这些结果有望加深我们对控制分子内和分子间电子转移速率和特异性的因素的理解。用于研究光合系统中电场效应的实验和理论方法将扩展到非生物系统。这些方法将用于测量(1)金属到配体的电荷转移和过渡金属配合物的价间跃迁中的电荷分离程度，(2)外加电场对供体和受体之间电子耦合的影响，(3)发生电子转移但其吸收光谱不受受体存在影响的供体-受体化合物激发态中的电荷转移性质的程度；(4)电场对电子转移反应速率或竞争发光的影响；(5)不同聚合物基质的内场校正幅度。

In this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program the effects of applied electric fields on the absorption and emission spectra of a wide range of molecules, and on the rates of electron transfer reactions, will be examined. The results are expected to deepen our understanding of the factors which govern the rates and specificity of transfer of electrons within and between molecules. Experimental and theoretical methods which have been developed for studying the effects of electric fields in photosynthetic systems will be extended to non-biological systems. These approaches will be used to measure (1) the degree of charge separation in metal-to-ligand charge transfer and intervalence transitions in transition metal complexes, (2) the effects of applied electric fields on the electronic coupling between the donor and acceptor, (3) the degree of charge-transfer character in the excited states of donor-acceptor compounds which undergo electron transfer but whose absorption spectra are unaffected by the presence of the acceptor, (4) the effects of electric fields on the rates of electron transfer reactions or competing luminescence, and (5) the magnitude of the internal field correction for various polymeric matrices.