暗分子云模型中芳香化学对气相动力学的敏感性分析

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2024-10-21 DOI:10.1039/d4cp03229b
Alex N. Byrne, Ci Xue, Troy Van Voorhis, Brett A. McGuire
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引用次数: 0

摘要

在星际介质中探测到的复杂有机分子越来越多,这就需要建立可靠的动力学模型来研究相关的化学过程。此类模型需要为成千上万个反应中的每一个反应提供速率系数;这些速率系数的值通常是估算或推断出来的,从而导致很大的不确定性,而这些不确定性很少被量化。我们对三相乌云模型中的气相速率系数进行了全局蒙特卡罗分析和更局部的一次性敏感性分析。使用四种指标计算了随时间变化的敏感性,以确定整个网络的关键反应,特别是氰基萘分子的反应。所有四种指标都发现,涉及启动碳氢化合物增长的小型活性物种的反应对整个网络有很大影响。氰基萘对这些反应中的许多反应以及苯基阳离子(C6H5+)的环状形成和从苯到萘的芳香族增长最为敏感。今后的工作应优先考虑限制关键反应的速率系数,并扩大围绕这些过程的网络。这些结果凸显了灵敏度分析技术在确定复杂化学网络(如天体化学建模中常用的网络)中关键过程方面的优势。
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Sensitivity analysis of aromatic chemistry to gas-phase kinetics in a dark molecular cloud model
The increasingly large number of complex organic molecules detected in the interstellar medium necessitates robust kinetic models that can be relied upon for investigating the involved chemical processes. Such models require rate coefficients for each of the thousands of reactions; the values of these are often estimated or extrapolated, leading to large uncertainties that are rarely quantified. We have performed a global Monte Carlo and a more local one-at-a-time sensitivity analysis on the gas-phase rate coefficients in a 3-phase dark cloud model. Time-dependent sensitivities have been calculated using four metrics to determine key reactions for the overall network as well as for the cyanonaphthalene molecule in particular, an important interstellar species that is severely under-produced by current models. All four metrics find that reactions involving small, reactive species that initiate hydrocarbon growth have large effects on the overall network. Cyanonaphthalene is most sensitive to a number of these reactions as well as ring-formation of the phenyl cation (C6H5+) and aromatic growth from benzene to naphthalene. Future efforts should prioritize constraining rate coefficients of key reactions and expanding the network surrounding these processes. These results highlight the strength of sensitivity analysis techniques to identify critical processes in complex chemical networks, such as those often used in astrochemical modeling.
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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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