New Directions in Molecular Scattering: Multiple Pathways and Products

分子散射的新方向：多种途径和产品

• 批准号: EP/T021675/1
• 负责人: Kenneth McKendrick
• 金额: $ 749.25万
• 依托单位: Heriot-Watt University
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FT021675%2F1
• 关键词: New; Directions; Molecular; Scattering; Multiple

Colliding pairs of molecules in vacuum has become a uniquely powerful method for investigating the fundamental mechanisms through which molecules interact and either exchange energy or chemically react. Scattering experiments of this type have reached a high level of sophistication. Theoretical modelling has progressed in parallel, allowing the forces that act between the molecules to be calculated increasingly accurately and providing rigour to the interpretation of the mechanisms. However, until recently, these advanced methods have only been able to treat small molecular systems, typically containing no more than three atoms and often with only one set of chemical products formed via a single mechanism.Our vision is to make a dramatic step-change to the field of molecular collisions by extending the range of systems that can be studied to those more typical of real-world applications. Building on a core of fundamental, benchmark studies, we will progress to challenging, previously intractable problems with common features of having multiple reaction pathways and multiple distinct outcomes. This opportunity can only be grasped now because of recent technical advances in experimental methods and conceptual developments in the underlying theory that exploit the exponential growth in available computing power. The Investigators represent a unique team with diverse, complementary experimental and theoretical expertise, drawn from the two centres of excellence for molecular scattering in the UK. We will tackle an ambitious programme under three parallel themes:1) Scattering to benchmark fundamental theory. There is an on-going vital need to continue the advance in scattering experiments towards the goal of controlling fully the quantum states, relative orientation and speed of the incoming molecules, and measuring equally fully the corresponding properties of the products. Such 'ultimate' experiments provide the most stringent tests of state-of the-art theoretical predictions. We will perform a series of experiments on collisions of small, highly reactive free radicals (NO, OH) with molecular partners. Complementary advances in theoretical methodology for the calculation of realistic potential energy surfaces, which encode the forces, will allow the observations to be compared against the predictions of advanced-level scattering calculations.2) Scattering for the atmosphere, combustion and plasma science. The chemistry in these environments is driven by highly reactive radicals, ions, or electrons, present at low concentrations but responsible for sequences of reactions that interconvert stable molecules. Some of the most important reactions take place at the interface between the gas phase and liquid or solid surfaces. The major outstanding challenges lie in understanding individual steps in which different products are formed via competing mechanisms. We will answer such questions for several key reaction systems. These include reactions of OH with volatile organic compounds; collisions of electrons with building blocks of DNA, other biomolecules and polycyclic aromatic hydrocarbons (PAHs); and collisions of OH and Cl, important atmospheric oxidants, with the surfaces of liquids representative of aerosol particles.3) Scattering for catalysis. Heterogeneous catalysis is used widely in industry and elsewhere to accelerate the rates of otherwise impractically slow reactions. The underlying mechanisms have in most cases remained unknown, so that optimisation of real-world catalytic processes has been largely through empirical trial-and-error. We will help to overcome this lack of mechanistic insight by investigating reactions on model, mixed transition-metal clusters that mimic the active sites in solid heterogeneous catalysts. We will also develop new scattering methods, based on energetic metal atoms, to characterise the surface structures of ionic liquids, central to their role in forms of multiphase catalysis.

在真空中碰撞分子对已经成为研究分子相互作用、交换能量或化学反应的基本机制的一种独特而强大的方法。这种类型的散射实验已经达到了很高的复杂程度。理论建模已经并行进行，使得分子之间的作用力能够得到越来越准确的计算，并为机理的解释提供了严谨的解释。然而，直到最近，这些先进的方法还只能处理小分子系统，通常只包含不超过三个原子，并且通常只有一套通过单一机制形成的化学产品。我们的愿景是通过将可以研究的系统的范围扩展到那些更典型的真实世界应用来使分子碰撞领域发生戏剧性的变化。在基础基准研究的核心基础上，我们将进步到具有挑战性的、以前难以解决的问题，具有多个反应途径和多个不同结果的共同特征。只有现在才能抓住这个机会，因为最近实验方法的技术进步和基本理论的概念发展利用了可用计算能力的指数增长。研究人员代表着一个独特的团队，他们拥有不同的、互补的实验和理论专业知识，来自英国分子散射的两个卓越中心。我们将在三个平行主题下处理一项雄心勃勃的计划：1)分散到基准基础理论。有必要继续推进散射实验，以实现完全控制量子态、入射分子的相对取向和速度，以及同样充分地测量产物的相应性质的目标。这样的“终极”实验为最先进的理论预测提供了最严格的测试。我们将进行一系列关于小的、高活性的自由基(NO，OH)与分子伙伴的碰撞的实验。在计算真实势能面(编码力)的理论方法方面的互补进步，将使观测结果能够与高级散射计算的预测进行比较。2)大气、燃烧和等离子体科学的散射。这些环境中的化学是由高活性的自由基、离子或电子驱动的，这些自由基、离子或电子存在于低浓度，但负责相互转化稳定分子的一系列反应。一些最重要的反应发生在气相和液体或固体表面之间的界面上。主要的突出挑战在于了解通过竞争机制形成不同产品的各个步骤。我们将为几个关键的反应系统回答这样的问题。这些包括羟基与挥发性有机化合物的反应；电子与DNA、其他生物分子和多环芳烃(PAHs)的碰撞；以及重要的大气氧化剂--羟基和氯与代表气溶胶微粒的液体表面的碰撞。多相催化被广泛应用于工业和其他领域，以加快原本不可能实现的缓慢反应的速度。在大多数情况下，潜在的机制仍不清楚，因此，现实世界催化过程的优化主要是通过经验的反复试验。我们将通过研究模拟固体多相催化剂中活性中心的混合过渡金属簇合物上的反应来帮助克服这种缺乏机理洞察力的问题。我们还将开发基于高能金属原子的新散射方法来表征离子液体的表面结构，这对它们在多相催化形式中的作用至关重要。

项目成果

The Value of Different Experimental Observables: A Transient Absorption Study of the Ultraviolet Excitation Dynamics Operating in Nitrobenzene.

• DOI: 10.1021/acs.jpca.3c02654
• 发表时间: 2023-08-10
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY A
• 影响因子: 2.9
• 作者: Crane, Stuart W.;Garrow, Malcolm;Lane, Paul D.;Robertson, Kate;Waugh, Alex;Woolley, Jack M.;Stavros, Vasilios G.;Paterson, Martin J.;Greaves, Stuart J.;Townsend, Dave
• 通讯作者: Townsend, Dave

The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides.

• DOI: 10.1021/acs.orglett.3c02673
• 发表时间: 2023-09-22
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Broumidis, Emmanouil;Thomson, Christopher G.;Gallagher, Brendan;Sotorrios, Lia;Mckendrick, Kenneth G.;Macgregor, Stuart A.;Paterson, Martin J.;Lovett, Janet E.;Lloyd, Gareth O.;Rosair, Georgina M.;Kalogirou, Andreas S.;Koutentis, Panayiotis A.;Vilela, Filipe
• 通讯作者: Vilela, Filipe

The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2${\rm{Au}_{2}^{+}} {\rm{N}_{2}} $ and Au2+N2O${\rm{Au}_{2}^{+}} {\rm{N}_{2}{\rm{O}}} $

• DOI: 10.1002/ntls.20220023
• 发表时间: 2022-08
• 期刊: Natural Sciences
• 作者: M. Förstel;Nima‐Noah Nahvi;Kai Pollow;T. Studemund;Alice E. Green;A. Fielicke;S. Mackenzie;O. Dopfer

Efficient Computation of Two-Electron Reduced Density Matrices via Selected Configuration Interaction.

通过选定的配置相互作用有效计算二电子约简密度矩阵。

• DOI: 10.1021/acs.jctc.2c00738
• 发表时间: 2022-11-08
• 期刊: JOURNAL OF CHEMICAL THEORY AND COMPUTATION
• 影响因子: 5.5
• 作者: Coe, Jeremy P.;Carrascosa, Andres Moreno;Simmermacher, Mats;Kirrander, Adam;Paterson, Martin J.
• 通讯作者: Paterson, Martin J.

Time-Resolved X-ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS$_2$ Probed at the S 2p Edge

时间分辨 X 射线光电子能谱：在 S 2p 边缘探测 CS$_2$ 中的超快动力学

• DOI: 10.3204/pubdb-2023-05122
• 发表时间: 2023
• 作者: Gabalski I