Ab Initio Methods for Chiroptical Properties of Molecules in Solution

溶液中分子手性光学性质的从头计算方法

• 批准号: 1058420
• 负责人: Thomas Crawford
• 金额: $ 42.18万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-08-15 至 2015-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1058420&HistoricalAwards=false
• 关键词: Ab; Initio; Methods; Chiroptical; Properties

T. Daniel Crawford of Virginia Polytechnic Institute and State University is supported by the Chemical Theory, Models and Computational Methods Program in Chemistry and the Office of Cyberinfrastructure to develop methods that provide accurate predictions of the optical properties of chiral molecules in solution. The methods are based on coupled cluster linear response theory extended to incorporate solvent perturbations via both explicit and implicit models. This approach is systematically testable and convergent, benefitting from reduced-scaling implementations under development in the Crawford group that allow calculations involving many dozens of atoms. Applications include calculations of solution-phase optical rotation and circular dichroism spectra, and direct comparison with experiment. Results of this research include new chemical models that are embodied in sustainable software made freely available through the open-source PSI program package. The research provides valuable insight into the assignment of the absolute stereochemistry of natural products, as well as into the fundamental connections between molecular structure and the optical properties of chiral molecules. Educational efforts are directed towards training the next generation of computational scientists and the continued development of undergraduate computational laboratory experiments.

弗吉尼亚理工学院和州立大学的T. Daniel Crawford在化学化学理论、模型和计算方法项目和网络基础设施办公室的支持下，开发了能够准确预测溶液中手性分子光学性质的方法。该方法基于耦合簇线性响应理论，通过显式和隐式模型扩展到溶剂型扰动。这种方法是可系统地测试和收敛的，受益于Crawford小组正在开发的允许涉及几十个原子的计算的缩小规模的实现。应用包括溶液旋光度和圆二色光谱的计算，以及与实验的直接比较。这项研究的结果包括新的化学模型，这些模型体现在通过开源PSI程序包免费提供的可持续软件中。该研究为天然产物的绝对立体化学分配以及分子结构与手性分子光学性质之间的基本联系提供了有价值的见解。教育工作的目标是培养下一代计算科学家和继续发展本科计算实验室实验。