Theoretical Studies of Inorganic, Organometallic, and Bioinorganic Systems

通过这一由化学系化学结构、动力学和机制计划资助的奖项，德克萨斯农工大学的Michael B.Hall教授将使用现代量子力学计算来解决当前对催化反应或催化循环的基本步骤感兴趣的问题，包括烷烃和氢气的活化。采用非局域密度泛函理论的全梯度几何优化和从头算能量计算，主要是耦合的团簇和多参考组态相互作用，将是主要的计算工具。这项研究将研究天然酶系统，特别是氢酶系统，以及完全合成的系统，包括氢酶系统的模型络合物，以及激活烷烃和二氢的系统的热和光化学激活。该项目将涉及与实验小组的密切合作。这些前沿问题也为新的功能和方法发展提供了试验场。在这方面，计划了两个发展：一个是广义分子轨道方法，这是一种有限活动空间自洽场方法，用于初始化多参考组态相互作用；另一个是关于“Fenske-Hall”近似分子轨道方法。Fenske-Hall方法将被扩展，以探索其在量子力学/分子力学组合计算中的适用性。它的发展将在模拟金属酶和可能小到纳米晶体大小的金属簇合物方面特别有用。通过协作安排理论和实验的紧密结合将促进在这些重要化学问题上的快速进展。烷烃活化可以在更好地利用这些基本原材料方面发挥作用，了解自然和人工系统如何裂解和重组氢可以帮助发展氢经济。除了为德克萨斯农工大学的学生和博士后提供教育外，现在与该实验室相关的大量合作者将教育方面带给了更广泛的受众。除了开发Fenske-Hall方法的智力价值外，其简单的图形用户界面(GUI)将得到扩展，以便更广泛的受众轻松使用该方法，并将其纳入本科生和研究生的化学键概念教学。

Through this award funded by the Chemical Structure, Dynamics, and Mechanisms Program of the Division of Chemistry, Professor Michael B. Hall at Texas A&M University, College Station, will solve problems of current interest in catalytic reactions or in fundamental steps of catalytic cycles involving the activation of alkanes and dihydrogen by using modern quantum mechanical calculations. Full-gradient geometry optimizations with non-local density-functional theory and ab initio energy calculations, primarily coupled cluster and multireference configuration interaction, will be the primary computational tools. The research will study both natural enzymatic systems, particularly the hydrogenase enzymes, and totally synthetic systems, including model complexes for the hydrogenase systems and both thermal and photochemical activation of the systems that activate alkanes and dihydrogen. The project will involve close collaborations with experimental groups. These frontier problems also provide a testing ground for new functional and methodological developments. In that regard two developments are planned: one on the generalized molecular orbital method, which is a restricted-active-space self-consistent-field method to initialize multireference configuration interaction, and another on the "Fenske-Hall" approximate molecular orbital method. The Fenske-Hall method will be expanded to explore its applicability to combined quantum-mechanical/molecular-mechanical calculations. Its development will be particularly useful in modeling metalloenzymes and in metallo-clusters possibly as large as small nanocrystals. The close coupling of theory and experiment through collaborative arrangements will stimulate rapid progress on these important chemical problems.Alkane activation can play a role in making better use of these basic raw materials, and understanding how nature and artificial systems cleave and reassemble hydrogen can help in the development of a hydrogen economy. In addition to the education of students and postdoctoral associates at Texas A&M University, the large number of collaborators now associated with the laboratory brings the educational aspects to a much broader audience. In addition to the intellectual value in the development of the Fenske-Hall method, its simple graphical users interface (GUI) will be expanded to allow the method to be easily used by a wider audience and to be incorporated into teaching both undergraduate and graduate students about chemical bonding concepts.