RUI: A Theoretical Investigation of Multireference Diradical Molecules

RUI：多参考双自由基分子的理论研究

• 批准号: 0809462
• 负责人: Carol Parish
• 金额: $ 26.74万
• 依托单位: University of Richmond
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-08-15 至 2012-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0809462&HistoricalAwards=false
• 关键词: RUI; Theoretical; Investigation; Multireference; Diradical

Carol Parish of the University of Richmond is supported by a Research in Undergraduate Institutions (RUI) award from the Theoretical and Computational Chemistry program for theoretical investigations of cyclization reactions involving radical intermediates. The work is focused on 1) Utilizing and comparing the Spin-Flip, Singlet-type Strongly Orthogonal Geminal (SSG), Multireference Averaged-Quadratic Coupled Cluster (MR-AQCC) and Completely Renormalized Coupled Cluster (CR-CC(2,3)) methods for describing the multireference character, energies and structures of diradicals; 2) Applying one or more of these methods to the characterization of novel electro-cyclization reactions involving diradical intermediates; 3) Investigating reactions involving tetraradicals; 4) Using the force field based hybrid Monte Carlo-Low Mode method of conformational analysis to evaluate the ensemble of structures for larger natural product diradical precursors; 5) Developing algorithms for using Kohonen's self-organizing map to evaluate the geometrical clustering properties of ensembles, and; 6) Employing the KNIME scripting language to provide "wrappers" to facilitate the use of these methods by undergraduates.The ability to characterize properly open-shell radical species and the corresponding investigation of novel cyclization reactions holds significant promise for advancing the fields of multireference theoretical chemistry, mechanistic organic chemistry, materials design and drug optimization. This work is contributing to furthering understanding of radical behavior and is expected to positively impact these fields of application. The work is being performed by undergraduate researchers as early as their first year of study. The students are receiving intensive training in computational chemistry, and, from this experience, are developing skill sets that will serve them well in their post-baccalaureate scientific careers. The PI is a founding member of the MERCURY consortium which was designed to mentor new computational and theoretical chemistry faculty at other predominately undergraduate institutions in achieving teaching and research excellence. Students involved in this project are participating in MERCURY activities, further broadening the impact of this project.

里士满大学的Carol Parish得到了理论和计算化学项目颁发的本科院校研究奖(RUI)的支持，该奖项旨在对涉及自由基中间体的环化反应进行理论研究。1)利用并比较了自旋翻转、单重态强正交Geminal(SSG)、多参考平均-二次耦合簇(MR-AQCC)和完全重整化耦合簇(CR-CC(2，3))方法来描述双自由基的多参考性质、能量和结构；2)将这些方法中的一种或多种应用于表征涉及双自由基中间体的新型电环化反应；3)研究了涉及四环芳烃的反应；4)使用基于力场的混合蒙特卡罗-低模式构象分析方法来评估较大天然产物双自由基前驱体的结构集合；5)开发使用Kohonen的自组织映射来评估系综的几何聚集性质的算法；6)使用Knime脚本语言提供“包装器”，以方便本科生使用这些方法。正确表征开壳自由基物种的能力以及相应的新型环化反应的研究对于促进多参考理论化学、机械有机化学、材料设计和药物优化领域的发展具有重要意义。这项工作有助于加深对激进行为的理解，并有望对这些应用领域产生积极影响。这项工作是由本科生研究人员在他们学习的第一年就开始进行的。这些学生正在接受计算化学的强化培训，并从这次经历中发展出一整套技能，这些技能将为他们在毕业后的科学生涯中提供良好的服务。该协会是水星联盟的创始成员之一，该联盟旨在指导其他以本科生为主的机构的新计算和理论化学教员实现卓越的教学和研究。参与该项目的学生正在参与水星活动，进一步扩大了该项目的影响。