Donor-Acceptor Electronic Coupling at Long and Short Range

这个无机、生物无机和有机金属化学项目的奖项支持加州理工学院的Harry B. Gray、Bruce S. Brunschwig和Jay R. Winkler教授研究调节供体和受体之间电子耦合相互作用的因素。通过玻璃化溶剂的电子隧穿研究将探测远程（弱耦合）系统，而短程相互作用（强耦合D-A配合物）将使用斯塔克光谱进行研究。特别是，对温度依赖性的详细研究将探讨非康顿效应在无序介质中促进ET的作用。对D-A电子耦合的更好理解将有助于揭示控制生物系统中电子流的因素，也将有助于有机半导体和电子器件的发展。本研究计划将检验超交换耦合模型的有效性，并从经验上阐明电子耦合距离衰减因子对桥接介质的电子和结构性质的依赖。通过玻璃化溶剂的电子隧穿的研究应该提供远程电子耦合相互作用的关键见解。Stark光谱学已被选择作为解释强耦合D-A配合物中的短程耦合的选择方法。自20世纪80年代末第一个有机场效应晶体管的发展以来，人们对在电子器件中使用有机分子的兴趣越来越大。通过有机介质的电子传递在这些器件中起着核心作用，因此提出的研究可能为改进这些器件提供关键的新见解。学生将接受无机化学和物理化学以及生物学应用方面的培训。他们还将参加高级无机化学专题课程，该课程将外部访客、教师、博士后、研究生和本科生聚集在一起，就物理无机化学的当前主题进行广泛、深入的讨论。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professors Harry B. Gray, Bruce S. Brunschwig and Jay R. Winkler at the California Institute of Technology to examine factors that modulate electronic coupling interactions between donors and acceptors. Studies of electron tunneling through vitrified solvents will probe long-range (weakly coupled) systems, while short-range interactions (strongly coupled D-A complexes) will be investigated using Stark spectroscopy. In particular, detailed investigations of temperature dependences will probe the role of non-Condon effects in promoting ET in disordered media. A better understanding of D-A electronic couplings will shed new light on the factors that control electron flow in biological systems and also will aid the development of organic semiconductors and electronic devices. This research program will test the validity of superexchange coupling models and elucidate empirically the dependence of electronic coupling distance decay factors on the electronic and structural properties of the bridging medium. Studies of electron tunneling through vitrified solvents should provide key insights into long-range electronic coupling interactions. Stark spectroscopy has been selected as the method of choice to elucidate short-range couplings in strongly coupled D-A complexes. Since the development of the first organic field effect transistor in the late 1980s, there has been increasing interest in using organic molecules in electronic devices. Electron transport through organic media plays a central role in these devices, so that the proposed research may provide critical new insights to improve these devices. Students will receive training in inorganic and physical chemistry together with applications in biology. They will also participate in a special topics course in advanced inorganic chemistry, which brings together outside visitors, faculty, postdocs, graduate students, and undergraduates for wide ranging, in-depth discussions of current topics in physical inorganic chemistry.