卤化氢共振增强多光子电离光谱

测定了卤化氢(HCl, HBr 和HI) (2+1)共振增强多光子电离(REMPI)光谱, 采用模拟计算法分析推导出转动常数、谱带源以及Ω态振动谱带的同位素位移值. 得到的HCl数据同Green等人用常规分析法所推导的结果极为吻合. 得出8条振动谱带,其中包括V(¹∑⁺)态, E(¹∑⁺)的v'=4态以及HBr的5个新谱带, 此外还推导出HI的E态v'=1的4个振动谱带光谱参数. 观测了V和E态之间因同类相互作用而产生的不规则能级间距、转动参数和同位素位移. 讨论了HCl和HBr的E态和V态振动谱带中的转动谱线序列O和S对Q的强度比变化,提出了双光子激发机理.

REMPI Spectra of the Hydrogen Halides

(2+1) Resonance multiphoton ionization (REMPI) spectra of HX(X=Cl, Br and I) were recorded and analyzed by simulation calculation to derive rotational constants, band origins and isotope shift values for a number of vibrational bands of Ω states. Our data for HCl compared nicely with those derived by Green et al. using conventional analysis methods. Newspectroscopic parameters were derived for 8 vibrational bands which were assigned to the V(¹∑⁺) state, for v'=4 of the E(¹∑⁺) state as well as for 5 new bands in HBr . New spectroscopic parameters were derived for 4 vibrational bands which are assigned to the V state and for v'=1 of the E state in HI. Anomalies in energy level spacings, rotational parameters and isotope shift values were observed as being largely due to homogeneous interactions between the V and the E states. Variations observed in the intensity ratio of O and S line series to Q line series in vibrational bands of the E and V states for HCl and HBr were discussed and mechanisms of two photon excitation processes were proposed.