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

Harvey Mudd学院的Hal van Ryswyk和Robert Cave教授得到了无机、无机和有机金属化学项目的支持，他们对一系列混合价金属卟啉二聚体的电子耦合进行了实验和理论研究，这些二聚体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，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。理论方法应用Koopman定理-广义Mulliken-Hush方法（KT-GMH），通过基于半经验、Hartree-Fock和密度泛函理论的方法计算这些系统的耦合元素。这种实验和理论的合作将导致对这些系统的电荷转移特性的详细了解，并为KT-GMH方法提供严格的测试。研究结果将为新型材料、仿生模型和催化剂的研制提供坚实的基础。开发新的理论化学工具，通过实验模型进行彻底测试，是提高我们对大规模电荷转移系统理解的关键一步。该奖项研究的金属卟啉低聚物具有广泛的材料科学应用前景，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。本科生将在材料合成和表征以及金属卟啉二聚体和三聚体的电子结构计算方面接受多方面的培训。

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.