Ab Initio Methods for Chiroptical Properties of Molecules in Solution

弗吉尼亚理工学院和州立大学的T.Daniel Crawford得到了化学中的化学理论、模型和计算方法计划以及网络基础设施办公室的支持，以开发能够准确预测溶液中手性分子光学性质的方法。该方法基于耦合团簇线性响应理论，通过显式和隐式两种模型扩展以考虑溶剂扰动。这种方法是系统可测试和收敛的，得益于Crawford小组正在开发的缩小比例实现，允许涉及数十个原子的计算。应用包括溶液相旋光和圆二色谱的计算，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，这些模型体现在可持续软件中，可通过开源PSI程序包免费获得。这项研究为天然产物的绝对立体化学的归属以及手性分子的分子结构和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生计算实验室实验。

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.