Institute for Lasers, Life and Biophotonics Amsterdam, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
J Chem Phys. 2010 Oct 14;133(14):144317. doi: 10.1063/1.3502471.
The 3pπD (1)Π(u) state of the H(2) molecule was reinvestigated with different techniques at two synchrotron installations. The Fourier transform spectrometer in the vacuum ultraviolet wavelength range of the DESIRS beamline at the SOLEIL synchrotron was used for recording absorption spectra of the D (1)Π(u) state at high resolution and high absolute accuracy, limited only by the Doppler contribution at 100 K. From these measurements, line positions were extracted, in particular, for the narrow resonances involving (1)Π(u) (-) states, with an accuracy estimated at 0.06 cm(-1). The new data also closely match multichannel quantum defect calculations performed for the Π(-) components observed via the narrow Q-lines. The Λ-doubling in the D (1)Π(u) state was determined up to v=17. The 10 m normal incidence scanning monochromator at the beamline U125/2 of the BESSY II synchrotron, combined with a home-built target chamber and equipped with a variety of detectors, was used to unravel information on ionization, dissociation, and intramolecular fluorescence decay for the D (1)Π(u) vibrational series. The combined results yield accurate information on the characteristic Beutler-Fano profiles associated with the strongly predissociated Π(u) (+) parity components of the D (1)Π(u) levels. Values for the parameters describing the predissociation width as well as the Fano-q line shape parameters for the J=1 and J=2 rotational states were determined for the sequence of vibrational quantum numbers up to v=17.
利用两种不同的同步加速器装置,对 H(2)分子的 3pπD (1)Π(u) 态进行了重新研究。SOLEIL 同步加速器的 DESIRS 光束线上的真空紫外波长范围的傅里叶变换光谱仪用于以高分辨率和高绝对精度记录 D (1)Π(u) 态的吸收光谱,该精度仅受 100 K 时多普勒贡献的限制。从这些测量中,特别是对于涉及 (1)Π(u) (-) 态的窄共振,提取了谱线位置,其精度估计为 0.06 cm(-1)。新数据还与通过窄 Q 线观察到的 Π(-) 分量进行的多通道量子亏损计算非常吻合。D (1)Π(u) 态中的 Λ 双重性确定至 v=17。BESSY II 同步加速器 U125/2 光束线上的 10 m 正入射扫描单色仪,与自制的靶室和各种探测器相结合,用于揭示 D (1)Π(u) 振动系列的电离、离解和分子内荧光衰减的信息。综合结果提供了与 D (1)Π(u) 能级的强烈预离解 Π(u) (+) 宇称分量相关的特征 Beutler-Fano 轮廓的准确信息。对于 J=1 和 J=2 转动状态的预离解宽度以及 Fano-q 线形状参数描述的参数的值,对于振动量子数序列 up to v=17 进行了确定。