The dynamics of heterogeneous reactions at ice surfaces relevant to atmospheric, interstellar and hypergolic phenomena.

与大气、星际和自转现象相关的冰表面异质反应动力学。

• 批准号: RGPIN-2022-04602
• 负责人: Ayotte, Patrick
• 金额: $ 2.11万
• 依托单位: Université de Sherbrooke
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748648
• 关键词: dynamics; heterogeneous; reactions; ice; surfaces

The investigations described in this proposal rely on the preparation of metastable species using molecular beam techniques to study interfacial chemical dynamics of key heterogeneous atmospheric, hypergolic, and interstellar chemistry reactions. The first theme will exploit a recently developed methodology to prepare trans-ONONO2, a metastable isomer of the nitrogen dioxide dimer that was proposed to be a key reaction intermediate for NO2 hydrolysis, but also for prototypical hypergolic reactions with hydrazine, H2NNH2. These important reactions will be investigated within amorphous solid water/hydrazine, and at their surface, at temperatures where reaction intermediates can be trapped and characterized spectroscopically by exploiting electric field standing waves (EFSW) to enhance the specificity and sensitivity of reflection-absorption IR spectroscopy (RAIRS) providing valuable molecular-level insight into reaction mechanisms and their dynamics. Custom instrumentation will also be developed to allow for these investigations to be performed under environmentally relevant conditions while field studies of the photochemical NOx fluxes at the Canadian High Arctic Research Station (CHARS) will also be initiated. The second theme aims at improving our understanding of confinement effects on the interconversion between ortho and para nuclear spin isomers (NSI) of small molecules (H2O, NH3, C2H2, and H2CO) for magnetic resonance applications in surface science. The proposed investigations build upon our unique capabilities for the preparation of beams of these small molecules enriched in their metastable ortho NSI using magnetic focusing thereby allowing state-to-state NSI interconversion dynamics upon scattering at surfaces to be performed by resonance-enhanced multi-photon ionization time-of-flight mass spectrometry (REMPI-TOF-MS). As confinement of NSI upon their adsorption at surfaces triggers their interconversion, the erosion of the enrichment in their ortho NSI hampers potential magnetic resonance applications to surface science relying on spin polarized molecules. Confinement effects will also be investigated in endofullerenes as recent work showed that the ro-translational dynamics could yield very slow erosion in the NSI distributions of D216O@C60 as the confinement-induced inter- and inter-molecular couplings responsible for NSI interconversion may be strongly suppressed in these compounds.  Materials with enhanced retention of their nuclear spin isomers are highly desirable and could find applications in magnetic resonance spectroscopy and imaging as well as quantum information processing.  These two research themes will provide ample opportunities for HQP to be trained in advanced custom experimental, numerical simulations, and molecular modelling methods of molecular sciences, in a highly collaborative environment, that involves industrial and academic partners from around the world.

这项建议中描述的研究依赖于使用分子束技术制备亚稳态物种，以研究关键的非均相大气、自燃和星际化学反应的界面化学动力学。第一个主题将利用最近开发的方法来制备反式ONONO2，这是二氧化氮二聚体的一种亚稳态异构体，被认为是NO2水解的关键反应中间体，也是与联氨、H2NNH2的典型自燃反应的关键反应中间体。这些重要的反应将在无定形固体水/肼中进行研究，并在其表面通过利用电场驻波(EFSW)来增强反射吸收红外光谱(RAIRS)的特异性和灵敏度来进行光谱表征，从而在分子水平上深入了解反应机理及其动力学。还将开发定制仪器，以便在与环境有关的条件下进行这些调查，同时还将在加拿大北极高地研究站启动对光化学NOx通量的实地研究。第二个主题旨在提高我们对小分子(H2O、NH3、C2H2和H_2CO)的邻核和副核自旋异构体(NSI)之间相互转化的限制效应的理解，以用于表面科学中的磁共振应用。拟议的研究建立在我们独特的能力的基础上，使用磁聚焦来制备这些小分子的光束，这些小分子富含亚稳的邻位NSI，从而允许通过共振增强多光子电离飞行时间质谱仪(REMPI-TOF-MS)执行散射时的状态到状态NSI的相互转换动力学。由于NSI对它们在表面的吸附的限制触发了它们的相互转化，它们在邻位NSI中的浓缩的侵蚀阻碍了依赖于自旋极化分子的潜在的磁共振在表面科学中的应用。还将研究内富勒烯的限制效应，因为最近的工作表明，旋转平移动力学可以在D216O@C60的NSI分布中产生非常缓慢的侵蚀，因为导致NSI相互转化的限制诱导的分子间和分子间耦合可能在这些化合物中受到强烈抑制。具有增强的核自旋异构体保留的材料是非常可取的，可以在磁共振光谱和成像以及量子信息处理中找到应用。这两个研究主题将为HQP提供大量的机会，在一个高度合作的环境中，培训高级的定制实验、数值模拟和分子模拟方法，分子科学的高级定制实验、数值模拟和分子建模方法，包括来自世界各地的产业界和学术界的合作伙伴。