Periodic Coupled Cluster Methods for Optical Activity in Chiral Crystals

手性晶体光学活性的周期性耦合簇方法

• 批准号: 2154452
• 负责人: Marco Caricato
• 金额: $ 45.65万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154452&HistoricalAwards=false
• 关键词: Periodic; Coupled; Cluster; Methods; Optical

WIth support from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry, Marco Caricato of the University of Kansas will work to develop accurate quantum mechanical methods to simulate the electronic response of solids to external fields, with a direct application to optical activity. These methods are expected to provide highly accurate data for this important electronic property of chiral materials, with a twofold goal: to understand the elusive effect of intermolecular interactions on this property, and to benchmark and improve approximate but computationally efficient methods. Caricato will also develop interpretative tools for structure-property relations that may help define design principles for materials with desired features. These tools will be used to develop reduced-scaling strategies to increase computational efficiency. The broader impact of this proposal hinges on the use of computational chemistry to benefit society both in terms of technological advances and educational opportunities. A deeper understanding of the chiral response of a material may lead to design principles for the rational design of materials with desired properties for targeted applications in growing research fields such as chiral sensing and electronics. Caricato will also develop an outreach initiative to exploit the enormous potential of quantum chemistry simulations for high school education. In collaboration with local high school teachers, Caricato will develop educational modules where the students actively run the simulations and analyze the results. This initiative will hopefully stimulate the enthusiasm for science of high school students in rural and economically disadvantaged areas of the state of Kansas, and inspire them to pursue further training in STEM (science, technology, engineering and mathematics) disciplines. Under this award, the Caricato team will develop linear response-periodic coupled cluster (LR-PCC) methods for crystalline solids, and a tensor decomposition analysis useful for data interpretation as well as computational cost reduction. Although density functional theory (DFT) methods still represent a great compromise between cost and accuracy for solid state calculations, they still suffer from the same drawbacks as for molecules: the quality of the results is system-dependent and individual functionals are not systematically improvable. Particularly problematic is the description of intermolecular interactions, which are fundamental for the overall optical response of a chiral system in the condensed phase. The proposed LR-PCC methods will provide accurate data on the role of intermolecular interactions on the optical activity of solids as well as benchmarking data for the development of functionals and basis sets tailored for this property. At the same time, new approaches for qualitative analysis of the relevant tensors will be developed that may help unravel the elusive structure-property relations in optically active materials. These approaches will be also used to devise reduced-scaling techniques to increase the computational efficiency of the algorithms. These efforts have the potential to lead to general methodologies that can be applied to other electronic properties of solids beyond optical activity.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学理论，模型和计算方法项目的支持下，堪萨斯大学的Marco Caricato将致力于开发精确的量子力学方法来模拟固体对外场的电子响应，并直接应用于光学活性。预计这些方法将为手性材料的这一重要电子性质提供高度准确的数据，其目标有两个：了解分子间相互作用对该性质的难以捉摸的影响，以及基准测试和改进近似但计算效率高的方法。Caricato还将开发结构-性能关系的解释工具，这些工具可能有助于定义具有所需功能的材料的设计原则。这些工具将用于开发缩减比例的策略，以提高计算效率。这一提议的更广泛影响取决于使用计算化学在技术进步和教育机会方面造福社会。对材料的手性响应的更深入理解可以导致合理设计具有所需特性的材料的设计原理，用于在日益增长的研究领域（例如手性传感和电子学）中的目标应用。Caricato还将制定一项推广计划，以利用量子化学模拟在高中教育中的巨大潜力。Caricato将与当地高中教师合作开发教育模块，让学生积极运行模拟并分析结果。这一举措有望激发堪萨斯州农村和经济落后地区高中生对科学的热情，并激励他们在STEM（科学、技术、工程和数学）学科中继续深造。根据该奖项，Caricato团队将开发用于结晶固体的线性响应-周期耦合簇（LR-PCC）方法，以及用于数据解释和降低计算成本的张量分解分析。虽然密度泛函理论（DFT）方法仍然代表了固态计算的成本和精度之间的很大妥协，但它们仍然存在与分子相同的缺点：结果的质量取决于系统，并且单个泛函不能系统地改进。特别有问题的是分子间相互作用的描述，这是基本的整体光学响应的手性系统在凝聚相。拟议的LR-PCC方法将提供关于分子间相互作用对固体旋光活性的作用的准确数据，以及为开发针对此属性的泛函和基组提供基准数据。与此同时，相关张量的定性分析的新方法将被开发，这可能有助于解开光学活性材料中难以捉摸的结构-性质关系。这些方法也将被用来设计缩减尺度技术，以提高算法的计算效率。这些努力有可能导致一般的方法，可以应用到其他电子性质的固体光学activity.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。

项目成果

On the choice of coordinate origin in length gauge optical rotation calculations

长度计旋光计算中坐标原点的选择

• DOI: 10.1002/chir.23575
• 发表时间: 2023
• 期刊: Chirality
• 影响因子: 2
• 作者: Parsons, Taylor;Balduf, Ty;Caricato, Marco
• 通讯作者: Caricato, Marco