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    龙精明, 王华胜

    Resonance enhanced multiphoton ionization spectra of HCl:analysis of F1Δ2 spectral perturbation

    Long Jing-Ming, Wang Hua-Sheng
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    • 通过共振多光子电离-飞行时间法, 记录了氯化氢分子在84800-85700 cm-1范围内, F1Δ2 (v’=1) 里德堡态以及V1∑+ (v’=13, 14) 离子对态的电离产物H+, 35Cl+, H35Cl+ 及其同位素的光谱数据. 由于受离子对态V1∑+ 的作用, F1Δ2 (v’=1)态呈现出明显的近共振相互作用特性. 为了分析F1Δ2与V1∑+态之间存在的光谱微扰, 基于光解离电离通道的分析, 并针对F1Δ2 (v’=1)态离子信号比的变化, 将离子信号二能级作用模型优化到三能级的作用模型, 计算得到了微扰强度值为0.6 cm-1, 预解离系数γ为0.025. 此外, 对于F1Δ2 (v’=1) 与V1∑+ (v’=13, 14)态的三个振动能级的光谱峰位置, 采用光谱解微扰法拟合, 同样得到了类似的微扰强度和去微扰后的各光谱参数. 研究表明, 激发至F1Δ2 (v’=1)态得到的H+, Cl+ 离子主要是该态通过与离子对态耦合作用而产生, 而F1Δ2 (v’=1) 态光谱位置偏移不仅受离子对态而且还受其他里德堡态作用的影响. 同时, 非零γ 值证实了F1Δ2态预解离的存在.
      Spectra of H+, 35Cl+, H35Cl+ and their isotopologues, due to resonance enhanced multiphoton ionization (REMPI) of HCl via the F1Δ2 (v’=1) Rydberg and V1∑+ (v’=13, 14) ion-pair states are recorded in a range of 84800-85700 cm-1. Perturbation effects indicate the resonance interaction between the F1Δ2 (v’=1) and V1∑+ (v’=14) states. An improved model for analyzing relative signal intensity of spectrum, based on state interaction and photofragmentation process, is used to analyze the F1Δ2 (v’=1) spectral data. Interaction strength (W’=0.6 cm-1) and a predissociation parameter (γ=0.025) are derived. Comparable interaction strength and unperturbed spectroscopic parameters are derived from the deperturbation analysis of line positions for the F1Δ2 (v’=1) and V1∑+ (v’=13, 14) spectra. The study indicates that the formation of the H+ and Cl+ ions via two-photon resonance excitation of F1Δ2 (v’=1) state is associated with the state interaction. An indication of the line-shift of F1Δ2 (v’=1) state spectrum due to Rydberg-to-Rydberg state interaction is also found. The nonzero γ value suggests that the predissociation of the F1Δ2 state is important.
        • 基金项目:冰岛自然科学基金(批准号: 090046023)和冰岛大学研究基金资助的课题.
        • Funds:Project supported by Icelandic Science Foundation (Grant No. 090046023) and the Research Fund of University of Iceland.
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      • 被引次数:0
      出版历程
      • 收稿日期:2013-04-15
      • 修回日期:2013-05-03
      • 刊出日期:2013-08-05

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