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Rotationally Resolved Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron Vibrational Bands for H2+(X2§+g , v+=0-18)
Chao Chang,Cheuk-Yiu Ng*,S. Stimson,M. Evans,C. W. Hsu
Author NameAffiliationE-mail
Chao Chang Department of Chemistry, University of California, Davis, Davis, CA 95616, USA  
Cheuk-Yiu Ng* Department of Chemistry, University of California, Davis, Davis, CA 95616, USA cyng@chem.ucdavis.edu 
S. Stimson Ames Laboratory, USDOE and Department of Chemistry, Iowa State University, Ames, IA 50011, USA  
M. Evans Ames Laboratory, USDOE and Department of Chemistry, Iowa State University, Ames, IA 50011, USA  
C. W. Hsu Ames Laboratory, USDOE and Department of Chemistry, Iowa State University, Ames, IA 50011, USA  
Abstract:
We have obtained a rotationally resolved vacuum ultraviolet pulsed ˉeld ionization-photoelectron (VUV-PFI-PE) spectrum of H2 in the energy range of 15.30-18.09 eV, covering the ionization transitions H2+(X2§+g ,v+=0-18, N+=0-5)?H2(X1§+g , v00=0, J00=0-4). The assignment of the rotational transitions resolved inthe VUV-PFI-PE vibrational bands for H2+(X2§+g , v+=0-18) and their simulation using the Buckingham-Orr-Sichel (BOS) model are presented. Only the ¢N=N+?J00=0 and §2 rotational branches are observed in the VUV-PFI-PE spectrum of H2. However, the vibrational band is increasingly dominated by the 4N=0 rotational branch as v+ is increased. The BOS simulation reveals that the perturbation of VUV-PFI-PE rotational line intensities by near-resonance autoionizing Rydberg states is minor at v+?6 and decreases as v+ is increased. Thus, the rotationally resolved PFI-PE bands for H2+(v+?6) presented here provide reliable estimates of state-to-state cross sections for direct photoionization of H2, while the rotationally resolved PFI-PE bands for H2+(v+·5) are useful data for fundamental understanding of the near resonance autoionizing mechanism. On the basis of the rovibrational assignment of the VUV-PFI-PE spectrum of H2, the ionization energies for the formation of H2+(X2§+g , v+=0-18, N+=0-5) from H2+(X1§+g , v00=0,J00=0-4), the vibrational constants (!e, !e?e, !eye, and !eze), the rotational constants (Bv+, Dv+, Be,and ?e), and the vibrational energy spacings ¢G(v++1/2) for H2+(X2§+g , v+=0-18) are determined. With a signiˉcantly higher photoelectron energy resolution achieved in the present study, the precisions of these spectroscopic values are higher than those obtained in the previous photoelectron studies. As expected, the spectroscopic results for H2+(X2§+g , v+=0-18) derived from this VUV-PFI-PE study are in excellent agreement with high-level theoretical predictions.
Key words:  H2, Rotationally resolved, Vacuum ultraviolet, Pulsed ˉeld ionization, Photoelectron, Buckingham-Orr-Sichel, Spectrum simulation
FundProject:美国能源部 Contract No. W-7405-Eng-82
转动分辨的H2+ (X2Σ+g , v+=0-18)真空紫外脉冲场电离光电子谱
常超,伍灼耀*,S. Stimson,M. Evans,C. W. Hsu
摘要:
测量了氢气离子转动分辨的真空紫外脉冲场电离光电子谱.涵盖了15.30?18.09 eV能量范围内的H2+(X2§+g , v+=0?18,N+=0?5)?H2(X1§+g , v00=0, J00=0?4)的电离跃迁. 通过基于Buckingham-Orr-Sichel(BOS)模型的光谱拟合和对氢气离子振动带H2+(X2§+g ,v+=0?18)的转动光谱的分析, 发现实验上只观察到对应于¢N=N+-J00=0,§2的转动跃迁. 振动量子数v+ 越高,¢N=0的转动跃迁越占主导地位, 而转动谱线强度受邻
关键词:  氢气,真空紫外,脉冲场电离,光电子谱,光谱拟合
DOI:10.1088/1674-0068/20/04/352-364
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