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引用次数: 0
摘要
研究碰撞引起的分子激发需要事先确定碰撞伙伴的精确分析势能面。对于氰基多炔等碳链分子来说,这是一个长期存在的难题,导致缺乏与 He 碰撞诱发的 HC5N、HC7N、HC9N 等的速率系数。为了克服这一瓶颈,我们引入了一种新方法:渐进扩展径向角度网络(RANGE)。这种方法将构建原子序数相互作用势能与确定其分析形式结合起来。我们以 HC3N-He 分子复合物为参考,评估我们方法的可靠性,因为它的分析位势是通过各种方法推导出来的。此外,我们还应用 RANGE 方法构建了 HC5N-He 和 HC7N-He 的相互作用电势分析表征。对分析势的分析揭示了三个系统性趋势:(i) 各向异性随碳链长度的增加而增加;(ii) 局域最小值的数量与碳原子的数量相关;(iii) 最浅的局域最小值始终位于复合物解离极限以下的 ∼30 cm-1 处。利用与时间无关的量子力学密切耦合形式主义,我们简要估算了与 He 碰撞诱导 HC3N、HC5N 和 HC7N 激发的倾向规则。结果表明,这三个碰撞系统表现出相同的倾向规则,都倾向于 Δj = 2 转变。
Constructing potential energy surface for carbon-chain containing systems using the radial angular network with gradual expansion method.
Investigating molecular excitation induced by collisions requires the prior determination of accurate analytical potential energy surfaces for the colliding partners. For carbon-chain molecules, such as cyanopolyynes, this has been a longstanding challenge, resulting in the absence of rate coefficients for HC5N, HC7N, HC9N, and others, induced by collisions with He. To overcome this bottleneck, we introduce a new approach: the Radial Angular Network with Gradual Expansion (RANGE). This method jointly connects the construction of ab initio interaction potentials with the determination of their analytical forms. We use the HC3N-He molecular complex as a reference to assess the reliability of our method, given that its analytical potential has been derived using various methods. Additionally, we apply the RANGE approach to construct the analytical representation of the interaction potential for HC5N-He and HC7N-He. The analysis of the analytical potentials reveals three systematic trends: (i) the anisotropy increases with the length of the carbon chain, (ii) the number of local minima correlates with the number of carbon atoms, and (iii) the shallowest local minimum is consistently located at ∼30 cm-1 below the dissociation limit of the complex. Using the time-independent quantum mechanical close-coupling formalism, we briefly estimate the propensity rules governing the excitation of HC3N, HC5N, and HC7N induced by collisions with He. Consequently, the three collisional systems exhibit the same propensity rule, favoring Δj = 2 transitions.
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.