Theoretical Studies of Inorganic, Organometallic, and Bioinorganic Systems

无机、有机金属和生物无机系统的理论研究

• 批准号: 1300787
• 负责人: Michael Hall
• 金额: $ 30万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1300787&HistoricalAwards=false
• 关键词: Theoretical; Studies; Inorganic; Organometallic; Bioinorganic

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.

通过该奖项由化学划分的化学结构，动力学和机制计划资助，得克萨斯州A＆M大学的Michael B. Hall教授将解决当前对催化反应的兴趣或涉及催化循环的基本步骤的问题，这些催化周期涉及烷烃和二氢型的激活，并使用现代量子机械机械量。具有非本地密度功能性理论的全梯度几何优化，并且初始能量计算（主要是耦合群集和多方面配置相互作用）将是主要的计算工具。 该研究将研究天然酶系统，尤其是氢化酶酶，以及完全合成的系统，包括用于氢化酶系统的模型复合物，以及激活烷烃和二氢基因的系统的热和光化学激活。该项目将涉及与实验组的密切合作。这些边界问题还为新的功能和方法论发展提供了测试基础。 在这方面，计划了两个发展：一种是一种广义分子轨道方法，这是一种限制性空间自符合场方法，用于初始化多次构型相互作用，另一种是“ Fenske-Hall”近似分子轨道方法。 Fenske-hall方法将扩展，以探索其对组合量子力学/分子机械计算的适用性。 它的发育将在对金属酶和可能与小纳米晶体一样大的金属簇建模中特别有用。 通过协作安排的理论和实验的紧密耦合将刺激这些重要的化学问题上的快速进步。烷烃激活可以在更好地利用这些基本原材料方面发挥作用，并了解自然和人工系统如何切割和重新组装氢可以帮助开发氢经济体。 除了对德克萨斯农工大学的学生和博士后同事的教育外，与实验室相关的大量合作者还将教育方面带给了更广泛的受众。除了Fenske-Hall方法开发的智力价值外，其简单的图形用户界面（GUI）还将扩展，以允许更广泛的受众轻松使用该方法，并将其纳入教学本科生和研究生有关化学键合概念的教学。