D3SC: Dynamic Effects in Ordinary Organic Reactions in Solution
D3SC:溶液中普通有机反应的动态效应
基本信息
- 批准号:2102647
- 负责人:
- 金额:$ 50万
- 依托单位:
- 依托单位国家:美国
- 项目类别:Standard Grant
- 财政年份:2021
- 资助国家:美国
- 起止时间:2021-07-01 至 2024-06-30
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
In this project funded by the Chemical Structure, Dynamics, and Mechanism-B Program of the Chemistry Division, Professor Daniel A. Singleton of Texas A&M University will investigate “dynamic effects” in reaction mechanisms. These are experimental observations in reactions that can neither be predicted nor explained using the standard models for mechanisms. The proposed research has five aims related to dynamic effects. The first two aims would explore newly identified forms of dynamic effects, one resulting from localized molecular vibrations that can occur in reactions promoted by light and another that arises from a flaw in modern statistical rate theories. A third aim is to apply newly developed understanding of dynamic effects in solvent to reinterpret a large classical area of chemistry, specifically 20th century carbocation chemistry. In this broad field, it is suggested that old controversies arose from the use of mechanistic models that were too simplified. A fourth aim is to apply a technology that arises from a dynamic effect to learn about mechanisms that are hidden from current chemical approaches. The overarching aim is to develop a comprehensive chemical theory of dynamic effects by combining current theories with machine-learning. Overall, this project will impact at a fundamental and broad level the understanding of many classic chemical reactions, while providing new approaches to the development and control of reactions. Student training is a major goal of this research including with a good record of including women and members of underrepresented groups in science as part of the research team. Graduate and undergraduate students in the Singleton group undertake comprehensive projects, which lead to the development of diverse skills. These range from experimental organic chemistry and precision analytical measurements, to quantum chemistry, coding, molecular dynamics calculations, and machine learning. The Singleton group will also continue its program of developing and distributing to the community computational tools that aid the study of dynamic effects in reactions. The research will particularly investigate an indirect approach to the long-sought goal of vibrationally promoting specific reactions in complex molecules. The idea to be explored is that triplet photosensitizers of varying energies can provide a controllable amount of energy to localized regions in molecules. The project will also investigate a flaw in variational transition state theory in which the actual reaction path departs from that expected based on the potential energy surface, with the primary goal of identifying additional examples of reactions subject to this flaw. The third project aim is based on the proposal that historical controversies in carbocation chemistry have resulted from the unconsidered intermediacy of incompletely solvated structures. This idea will be explored within a series of prominent classical carbocation reactions. The fourth project aim is to use a recently developed application of a dynamic effect, “energy read-out,” to study key hidden steps in reactions involving alkoxy radicals. This idea is notably applicable to non-adiabatic proton coupled electron transfer (PCET) reactions where mechanisms are inaccessible through ordinary experimental and computational methods. The final aim is to modify transition state theory by partitioning the transition state into regions of dynamical outcome using machine learning. This includes the development of active-learning and precision-enhancing methods designed to ease the application of trajectories to dynamic effects, as well as the provision of these computational tools to the wider chemical community.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.
在这个由化学学部化学结构、动力学和机理b项目资助的项目中,德克萨斯农工大学的Daniel A. Singleton教授将研究反应机制中的“动态效应”。这些是对反应的实验观察,既不能预测,也不能用机制的标准模型来解释。本研究有五个与动态效应相关的目标。前两个目标将探索新发现的动态效应形式,一个是由光促进的反应中可能发生的局部分子振动引起的,另一个是由现代统计速率理论的缺陷引起的。第三个目标是应用新发展的对溶剂动力学效应的理解来重新解释化学的一个大的经典领域,特别是20世纪的碳正离子化学。在这个广泛的领域中,有人认为,旧的争论是由于使用过于简化的机械模型引起的。第四个目标是应用一种源于动态效应的技术来了解当前化学方法所隐藏的机制。总体目标是通过将当前理论与机器学习相结合,发展一种全面的动态效应化学理论。总的来说,这个项目将在基础和广泛的层面上影响对许多经典化学反应的理解,同时为反应的发展和控制提供新的方法。学生培训是这项研究的一个主要目标,包括在研究团队中包括女性和代表性不足的科学群体成员的良好记录。Singleton小组的研究生和本科生承担综合项目,这导致了各种技能的发展。这些范围从实验有机化学和精密分析测量,到量子化学,编码,分子动力学计算和机器学习。Singleton小组还将继续其开发和分发社区计算工具的计划,以帮助研究反应中的动态效应。该研究将特别研究一种间接方法,以实现长期寻求的振动促进复杂分子中的特定反应的目标。要探索的想法是,不同能量的三重态光敏剂可以为分子中的局部区域提供可控的能量。该项目还将研究变分过渡态理论中的一个缺陷,即实际反应路径偏离基于势能表面的预期,主要目标是确定受此缺陷影响的反应的其他例子。第三个项目目标是基于碳正离子化学的历史争议是由于未考虑不完全溶剂化结构的中介作用。这个想法将在一系列著名的经典碳正离子反应中进行探讨。第四个项目的目标是使用最近开发的动态效应应用“能量读出”来研究涉及烷氧基自由基的反应中的关键隐藏步骤。这个想法特别适用于非绝热质子耦合电子转移(PCET)反应,其机制无法通过普通的实验和计算方法获得。最终目的是通过使用机器学习将过渡状态划分为动态结果区域来修改过渡状态理论。这包括开发主动学习和提高精度的方法,旨在简化轨迹对动态效应的应用,以及向更广泛的化学社区提供这些计算工具。该奖项反映了美国国家科学基金会的法定使命,并通过使用基金会的知识价值和更广泛的影响审查标准进行评估,被认为值得支持。
项目成果
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