Line shape parameters of the first pure rotational R lines of CO in helium baths down to a few kelvins.

IF 3.1 2区 化学 Q3 CHEMISTRY, PHYSICAL Journal of Chemical Physics Pub Date : 2025-03-07 DOI:10.1063/5.0253846
Franck Thibault, Alexandra Viel, Kevin M Dunseath, Magnus Gustafsson
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Abstract

Close coupling calculations of line shape parameters have been performed for the first pure rotational R0(j = 0-4) lines of CO in helium baths at various temperatures. Besides the usual Lorentzian widths and shifts, we provide the complex Dicke parameters as well as the double power law temperature representation of all four parameters. In addition, we study the speed dependence of these parameters. The R0(0) and R0(1) theoretical thermally averaged collisional widths and shifts between 500 and about 15 K are in excellent agreement with the values reported in the literature. Below this temperature range, we confirm the persistent substantial disagreement that exists since 1985 between experimental and theoretical values. We thus focus on this regime, which is important for astrophysical applications, and we discuss various beyond-Voigt effects at low temperatures to try to understand this mismatch. We show that such mechanisms do not allow experimental widths and shifts to be reconciled with those from theory.

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氦浴中CO的第一个纯旋转R线的线形参数降至几开尔文。
对不同温度下氦浴中CO的第一个纯旋转R0(j = 0-4)谱线进行了线形参数的紧密耦合计算。除了通常的洛伦兹宽度和位移外,我们还提供了复杂的迪克参数以及所有四个参数的双幂律温度表示。此外,我们还研究了这些参数与速度的关系。R0(0)和R0(1)的理论热平均碰撞宽度和位移在500和大约15 K之间,与文献报道的值非常吻合。在此温度范围以下,我们确认自1985年以来实验值和理论值之间存在持续的实质性分歧。因此,我们将重点放在这个对天体物理学应用很重要的状态上,并讨论了低温下的各种超voigt效应,以试图理解这种不匹配。我们表明,这种机制不允许实验宽度和变化与那些从理论调和。
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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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