Advanced Quantum Mechanical Methods for the Chiroptical Properties of Molecules in Solution

溶液中分子手性光学性质的先进量子力学方法

• 批准号: 1465149
• 负责人: Thomas Crawford
• 金额: $ 45万
• 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: 2015
• 资助国家: 美国
• 起止时间: 2015-06-01 至 2019-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465149&HistoricalAwards=false
• 关键词: Advanced; Quantum; Mechanical; Methods; Chiroptical

T. Daniel Crawford of Virginia Tech University is supported by an award from the Chemical Theory; Models and Computational Methods program in the Chemistry Division to develop theoretical and computational methods for the accurate prediction of the optical properties of chiral molecules in solution remains a challenging task for computational chemistry. A chiral molecule is one in which there are two different versions that are identical in composition but which cannot be superimposed, much like human hands. The "left-handed" and "right-handed" molecules are mirror images of one another. Such molecules are optically active, they can rotate plane-polarized light either clockwise or counter-clockwise. Chiral molecules play an important role in many branches of chemistry, including the chemistry that governs the functioning of living beings. Crawford and his research group focus on the development of robust and efficient methods for computing the special "chiroptical" properties of these molecules, with the overarching goal of providing practical and reliable tools for assigning absolute stereochemical configurations of chiral compounds. These studies are invaluable in the elucidating the intimate relationship between molecular structure and chiroptical response and thus may provide the chemical community with a deeper understanding of the nature of optical activity. The best approach for modeling the intimidating complexity of solvent effects on molecular properties remains elusive, especially for chiroptical properties such as optical rotation (OR), circular dichroism (CD), vibrational Raman optical activity (ROA), and circularly polarized luminescence (CPL), which exhibit an exquisite sensitivity to environmental effects. This project focuses on the development of robust and efficient tools for the high accuracy modeling of chiroptical properties in the liquid phase, including implicit, explicit, and hybrid approaches. Implicit models will be developed to approximate the bulk solute-solvent interaction using both shape- and density- based cavities coupled with potentials derived self-consistently. Explicit solvation effects will be accounted for using a new hybrid QM/MM scheme, including a novel wave-function-embedded periodic approach. Efficient implementation of these models will rely heavily on emerging reduced-scaling methods, particularly within the coupled cluster linear-response approach for non-resonant optical activity.

T.弗吉尼亚理工大学的丹尼尔·克劳福德获得了化学理论奖的支持;化学部的模型和计算方法项目旨在开发用于准确预测溶液中手性分子光学性质的理论和计算方法，这仍然是计算化学的一项具有挑战性的任务。 手性分子是指有两种不同形式的分子，它们的组成相同，但不能重叠，就像人手一样。 “左手”和“右手”分子是彼此的镜像。 这种分子是光学活性的，它们可以顺时针或逆时针旋转平面偏振光。 手性分子在化学的许多分支中起着重要作用，包括控制生物功能的化学。 Crawford和他的研究小组专注于开发强大而有效的方法来计算这些分子的特殊“手性”性质，其总体目标是为指定手性化合物的绝对立体化学构型提供实用和可靠的工具。 这些研究对于阐明分子结构与手性响应之间的密切关系具有重要意义，从而可以为化学界提供对光学活性本质的更深入理解。模拟溶剂对分子性质影响的复杂性的最佳方法仍然难以捉摸，特别是对于手性性质，如旋光度（OR），圆二色性（CD），振动拉曼光学活性（罗阿）和圆偏振发光（CPL），它们对环境效应表现出灵敏度。 该项目的重点是开发强大而有效的工具，用于液相手性性质的高精度建模，包括隐式，显式和混合方法。 隐式模型将被开发，以近似的本体溶质-溶剂相互作用，使用形状和密度为基础的空腔，加上自洽导出的潜力。 显式溶剂化效应将占使用一个新的混合QM/MM计划，包括一个新的波函数嵌入周期性的方法。 这些模型的有效实施将在很大程度上依赖于新兴的缩小尺度的方法，特别是在耦合集群的线性响应方法的非共振光学活性。

项目成果

Basis Set Superposition Errors in the Many-Body Expansion of Molecular Properties

分子性质多体展开中的基组叠加误差

• DOI: 10.1021/acs.jpca.9b03864
• 发表时间: 2019
• 期刊: Journal of physical chemistry
• 作者: Peyton, Benjamin G. Crawford

Diagrammatic Coupled Cluster Monte Carlo

图解耦合聚类蒙特卡罗

• DOI: 10.1021/acs.jpclett.9b00067
• 发表时间: 2019
• 期刊: Journal of chemical theory and computation
• 影响因子: 5.5
• 作者: Scott, Charles