Theoretical Studies of Inorganic, Organometallic, and Bioinorganic Systems

通过这个奖项资助的化学结构，动力学，和化学部的机制计划，教授迈克尔B。霍尔在得克萨斯A M大学，学院站，将解决目前感兴趣的问题，在催化反应或在催化循环的基本步骤，涉及活化烷烃和二氢通过使用现代量子力学计算。全梯度几何优化与非局部密度泛函理论和从头算能量计算，主要耦合集群和多参考配置的相互作用，将是主要的计算工具。 该研究将研究天然酶系统，特别是氢化酶，以及完全合成的系统，包括氢化酶系统的模型复合物以及激活烷烃和二氢的系统的热和光化学活化。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的发展提供了试验场。 在这方面，计划进行两项发展：一项是关于广义分子轨道方法，这是一种用于初始化多参考组态相互作用的受限活性空间自洽场方法，另一项是关于“Fenske-Hall”近似分子轨道方法。 Fenske-Hall方法将被扩展，以探索其适用于结合量子力学/分子力学计算。 它的发展将是特别有用的建模金属酶和金属簇可能大到小纳米晶体。 通过合作安排将理论和实验紧密结合将刺激这些重要化学问题的快速进展。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新组装氢可以帮助发展氢经济。 除了在得克萨斯A M大学的学生和博士后的教育，大量的合作者，现在与实验室带来了教育方面更广泛的受众。除了在芬斯克-霍尔方法的发展中的智力价值外，其简单的图形用户界面（GUI）将被扩展，以使该方法易于被更广泛的受众使用，并被纳入本科生和研究生关于化学键合概念的教学中。

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.