0Experimental and Theoretical Investigation of Electronic Coupling in Metalloporphyrin Dimers and Trimers

教授哈尔货车Ryswyk和哈维·穆德学院的罗伯特·凯夫是由无机，无机和有机化学计划的支持，他们的联合实验和理论研究的电子耦合在一系列的混合价金属卟啉二聚体，这可以定制不同的耦合程度。 无机材料的合成将使用固相技术进行，然后进行光谱表征，包括斯塔克光谱，这些化合物的电荷转移带。 理论方法适用于Koopman的定理广义Mulliken-Hush方法（KT-GMH）计算这些系统的耦合元件的半经验，Hartree-Fock，密度泛函理论为基础的方法。 这种合作的实验和理论的努力将导致这些系统的电荷转移特性的详细了解，并提供严格的测试的KT-GMH方法。 这些结果将为新材料组分、仿生模型和催化剂提供更坚实的基础。通过实验模型彻底测试的新理论化学工具的发展是提高我们对大规模电荷转移系统理解的关键一步。 在该奖项下研究的金属卟啉低聚物是广泛的材料科学应用的有吸引力的候选者，在分子尺度电子学，传感器，光学器件和太阳能转换方案中具有潜在的用途。 本科生将接受材料合成和表征方面的多方面培训，以及金属卟啉二聚体和三聚体的电子结构计算。

Professors Hal van Ryswyk and Robert Cave of Harvey Mudd College are supported by the Inorganic, Inorganic and Organometallic Chemistry program for their joint experimental and theoretical research on electronic coupling in a series of mixed-valence metalloporphryin dimers, which can be tailored to vary the degree of coupling. Inorganic materials synthesis will be carried out using solid-phase techniques followed by spectroscopic characterization, including Stark spectroscopy, of the charge-transfer bands of these compounds. The theoretical approach applies the Koopman's Theorem-Generalized Mulliken-Hush approach (KT-GMH) to calculate the coupling elements for these systems by semiempirical, Hartree-Fock, and Density Functional Theory-based methods. This collaborative experimental and theoretical effort will lead to a detailed understanding of the charge transfer characteristics of these systems, and provide stringent tests of the KT-GMH approach. The results will provide a firmer basis for new materials components, biomimetic models, and catalysts.The development of new theoretical chemistry tools thoroughly tested by experimental models is a critical step toward improving our understanding of large-scale charge-transfer systems. The metalloporphyrin oligomers studied under this award are attractive candidates for a wide range of materials science applications, with potential uses in molecular scale electronics, sensors, optical devices, and solar energy conversion schemes. Undergraduate students will receive multifaceted training in materials synthesis and characterization together with electronic structure calculations of metalloporphorin dimers and trimers.