Furtenbacher Tibor, Hegedus Samuel T, Tennyson Jonathan, Császár Attila G
MTA-ELTE Complex Chemical Systems Research Group, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary.
Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UK.
Phys Chem Chem Phys. 2022 Aug 17;24(32):19287-19301. doi: 10.1039/d2cp02240k.
Detailed understanding of the energy-level structure of the quantum states as well as of the rovibronic spectra of the ethylidyne (CH) and the hydroxyl (OH) radicals is mandatory for a multitude of modelling efforts within multiple chemical, combustion, astrophysical, and atmospheric environments. Accurate empirical rovibronic energy levels, with associated uncertainties, are reported for the low-lying doublet electronic states of CH and OH, using the Measured Active Rotational-Vibrational Energy Levels (MARVEL) algorithm. For CH, a total of 1521 empirical energy levels are determined in the primary spectroscopic network (SN) of the radical, corresponding to the following seven electronic states: X Π, A Δ, B Σ, C Σ, D Π, E Σ, and F Σ. The energy levels are derived from 6348 experimentally measured and validated transitions, collected from 29 sources. For OH, the lowest four doublet electronic states, X Π, A Σ, B Σ, and C Σ, are considered, and a careful analysis and validation of 15 938 rovibronic transitions, collected from 45 sources, results in 1624 empirical rovibronic energy levels. The large set of spectroscopic data presented should facilitate the refinement of line lists for the CH and OH radicals. For both molecules hyperfine-resolved experimental transitions have also been considered, forming SNs independent from the primary SNs.
对于多种化学、燃烧、天体物理和大气环境中的众多建模工作而言，详细了解亚乙基（CH）和羟基（OH）自由基的量子态能级结构以及振转电子光谱至关重要。使用测量的活性转动 - 振动能级（MARVEL）算法，报告了CH和OH低能态双重态电子态的精确经验振转能级及其相关不确定性。对于CH，在该自由基的主要光谱网络（SN）中总共确定了1521个经验能级，对应于以下七个电子态：X Π、A Δ、B Σ、C Σ、D Π、E Σ和F Σ。这些能级源自从29个来源收集的6348个经实验测量和验证的跃迁。对于OH，考虑了最低的四个双重态电子态X Π、A Σ、B Σ和C Σ，对从45个来源收集的15938个振转跃迁进行仔细分析和验证后，得到了1624个经验振转能级。所呈现的大量光谱数据应有助于完善CH和OH自由基的谱线列表。对于这两种分子，还考虑了超精细分辨的实验跃迁，形成了独立于主要光谱网络的光谱网络。
