质子化恶唑酮的气相反应性:化学动力学模拟和基于图论的分析揭示了离子-分子复合物的重要性。

IF 3.1 2区 化学 Q3 CHEMISTRY, PHYSICAL
Ariel F Perez Mellor, Thomas Bürgi, Riccardo Spezia
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引用次数: 0

摘要

本研究利用多种内部能量下的化学动力学模拟,深入研究了质子化环二甘氨酸的草唑酮形式(OXA)的碎裂机制。我们将深入分析的重点放在具有代表性的 178 kcal/mol 总能量上,同时也在 127-187 kcal/mol 范围内进行了模拟。这种更广泛的能量取样揭示了状态群如何随着内能的增加而演变,使我们能够计算速率常数,然后利用之前引入的三态模型计算有效能量阈值[Perez Mellor 等人,J. Chem. Phys. 155, 124103 (2021)]。通过将分子几何图形转化为图形表示,我们系统地分析了破碎过程,并确定了在破碎动力学中起关键作用的关键中间产物和离子-分子复合物(IMC)。这项研究强调了由 IMC 形成驱动的 OXA 独特的异构化景观,这与之前报道的环状和线性形式的行为形成了鲜明对比[Perez Mellor 等人,J. Chem. Phys. 155, 124103 (2021)]。由此产生的碎片通道以其独特的能量阈值和分支比为特征,可以为实验观察到的现象提供分子解释。由于使用了我们基于图论的工具对轨迹进行了精确分析,我们得以指出 OXA 碎片的特殊行为,它不同于其他异构体。特别是 IMC 的重要作用,它对不同异构体结构的填充产生了影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Gas-phase reactivity of protonated oxazolone: Chemical dynamics simulations and graph theory-based analysis reveal the importance of ion-molecule complexes.

This study delves into the fragmentation mechanisms of the oxazolone form (OXA) of protonated cyclo-di-glycine using chemical dynamics simulations at multiple internal energies. While we focus our in-depth analyses on a representative total energy of 178 kcal/mol, we also performed simulations over the 127-187 kcal/mol range. This broader energy sampling reveals how the population of states evolves with increasing internal energy, enabling us to compute rate constants and then effective energy thresholds using a previously introduced three-state model [Perez Mellor et al., J. Chem. Phys. 155, 124103 (2021)]. By transforming molecular geometries into graph representations, we systematically analyze fragmentation processes and identify key intermediates and ion-molecule complexes (IMCs) that play a crucial role in fragmentation dynamics. The study highlights the distinct isomerization landscapes of OXA, driven by IMC formation, which contrasts with the previously reported behavior of cyclic and linear forms [Perez Mellor et al., J. Chem. Phys. 155, 124103 (2021)]. The resulting fragmentation channels are characterized by their unique energetic thresholds and branching ratios and can provide a molecular explanation of what was observed experimentally. Thanks to an accurate analysis of the trajectories using our graph-theory-based tools, it was possible to point out the particular behavior of OXA fragmentation, which is different from other isomers. In particular, the important role of IMCs is shown, which has an impact on populating different isomeric structures.

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来源期刊
Journal of Chemical Physics
Journal of Chemical Physics 物理-物理:原子、分子和化学物理
CiteScore
7.40
自引率
15.90%
发文量
1615
审稿时长
2 months
期刊介绍: The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance. Topical coverage includes: Theoretical Methods and Algorithms Advanced Experimental Techniques Atoms, Molecules, and Clusters Liquids, Glasses, and Crystals Surfaces, Interfaces, and Materials Polymers and Soft Matter Biological Molecules and Networks.
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