Microwave Measurements of Structures and Electronic Properties of Transition Metal Complexes and Radicals

有了这个实验物理化学项目的奖项， 亚利桑那大学的Stephen Kukolich教授将修改并使用脉冲束傅里叶变换微波光谱仪来测量过渡金属络合物，自由基和其他分子在5至18 GHz微波频谱区域的旋转跃迁频率。 本文提出了一种新的激光光解光源，用于测量有机金属自由基及其反应产物。 这将允许比大多数以前的系统更有效和选择性地产生这些自由基和反应产物。这项工作的总体目标包括三维气相结构，磁相互作用参数和四极耦合强度的测量。 这些测量被提议用于：a）过渡金属自由基和涉及这些自由基的反应产物，B）过渡金属二氢和二氢化物络合物，和c）与过渡金属化合物的弱结合络合物。 磁相互作用参数和四极耦合强度直接表征了电子的电荷分布。 量子力学（密度泛函理论）的计算将进行所有的复合物的研究。 实验工作与理论计算的协调有助于使测量更有效，提高我们对分子电子结构的理解，并为从头算，量子化学计算的改进提供指导方针和实验实例。 过渡金属配合物在化学工业、生物体系和无机化学的研究领域中非常重要。 每年使用涉及过渡金属催化剂的反应生产数百万吨化学产品。 生命系统中许多酶和转运蛋白的活性部位都含有过渡金属配合物。 无机化学的研究和研究的很大一部分集中在过渡金属配合物上，拟议的工作将为研究，工业和教育中使用的结构数据库提供新的贡献。 拟议的工作往往涉及较小的，？模特？复杂，但将提供与更大，更复杂的系统相关的结果。 过渡金属配合物精确的三维结构有助于理解反应机理。 化学和生物学中反应机理的成功建模往往依赖于准确可靠的实验结构信息。 通过与新的实验数据相关来改进计算方法和基组是有用的，因为计算是目前关于短寿命自由基或高能反应中间体的详细信息的唯一来源。 金属二氢配合物的研究可为改进储氢技术提供有用的信息。 研究生和本科研究生将学习化学，量子力学和方法的基础知识和计算机工作，微波电子学和通过直接参与拟议的项目进行物理测量所涉及的技术。 参与研究的人数不足的少数民族和中学教师，或非博士。大学生将积极寻求拟议的项目。

With this award from the Experimental Physical Chemistry program, the P.I., Professor Stephen Kukolich of the University of Arizona will modify and use a pulsed-beam, Fourier-transform microwave spectrometer to measure rotational transition frequencies for transition metal complexes, radicals, and other molecules in the 5 to 18 GHz region of the microwave spectrum. A new laser-photodissociation beam source will be constructed for measurements on organometallic radicals and their reaction products. This will allow more efficient and selective production of these radicals and reaction products, than most previous systems. The overall objectives of this work include measurements of the three-dimensional gas-phase structures, magnetic interaction parameters and quadrupole coupling strengths. These measurements are proposed for: a) transition metal radicals and reaction products involving these radicals, b) transition metal dihydrogen and dihydride complexes, and c) weakly-bound complexes with transition metal compounds. The magnetic interaction parameters and quadrupole coupling strengths directly characterize the electronic charge distributions. Quantum mechanical (Density Functional Theory) calculations will be carried out for all of the complexes studied. The coordination of experimental work with the theoretical calculations helps to make the measurements more efficient, improves our understanding of the electronic structure of molecules and provides guidelines and experimental examples for improvements in ab initio, quantum chemistry calculations. Transition metal complexes are very important in the chemical industry, in biological systems and as an area of study in inorganic chemistry. Millions of tons of chemical products are produced each year using reactions which involve transition metal catalysts. The active sites of many enzymes and transport proteins in living systems contain transition metal complexes. A large fraction of the research and study in inorganic chemistry is focused on transition metal complexes, and the proposed work will provide new contributions to the structural database that is used in research, industry and education. The proposed work will often involve smaller, ?model? complexes, but will provide results relevant to the larger, more complex systems. The accurate, three-dimensional structures for transition metal complexes, are helpful in understanding reaction mechanisms. Successful modeling of reaction mechanisms in chemistry and biology often depends on the accurate and reliable experimental structural information. Improving calculation methods and basis sets through correlation with new experimental data is useful because the calculations are presently the only source of detailed information on short-lived radicals or high-energy reaction intermediates. Studies of metal dihydrogen complexes may provide information which will be useful for improving hydrogen storage technology. Graduate and undergraduate research students will learn fundamentals of chemistry, quantum mechanics and methods and techniques involved in computer work, microwave electronics and making physical measurements through direct involvement in the proposed projects. Participation in the research by underrepresented minorities and a secondary school teacher, or non-Ph.D. college student will be actively sought for the proposed projects.