Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO(+) and vibrational resolution in NCO(.).
Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO(+) and vibrational resolution in NCO(.).
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DOI：
10.1063/1.4920951
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发表时间：
2015-05
期刊：
影响因子：
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通讯作者：
F. Holzmeier;M. Lang;I. Fischer;Xiaofeng Tang;B. K. Cunha de Miranda;C. Romanzin;C. Alcaraz;P. Hemberger
中科院分区：
文献类型：
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作者：
F. Holzmeier;M. Lang;I. Fischer;Xiaofeng Tang;B. K. Cunha de Miranda;C. Romanzin;C. Alcaraz;P. Hemberger
利用真空紫外同步辐射，记录了两种不稳定含氮物种HNCO和NCO的阈值光电子能谱（TPES）。两者都是燃烧过程中的中间体，并在从废气中去除氮氧化物方面发挥作用。在轨道电离模型的框架下，分析了HNCO（+）的TPES第一带的旋振结构，并将原带的解析结构归属于ΔK子带.离子化能为11.602 ± 0.005 eV，并通过Franck-Condon拟合分析了阳离子基态的振动结构。还观察到HNCO（+）的低激发态。在第二系列实验中，通过从氯异氰酸酯快速热解产生NCO自由基。X（+）（3）π（-）基态的电离能为11.76 ± 0.02 eV，α（+）（1）Δ态的电离能为12.93 ± 0.02 eV。振动结构观察到这两种状态，并通过Franck-Condon模拟分配频带。
The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO(+) was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO(+) were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X(+) (3)Σ(-) ground state was determined to be 11.76 ± 0.02 eV, while for the a(+) (1)Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations.