On the complexity of the absorption spectrum of molecular nitrogen

The spectral properties of molecular nitrogen are crucial to a better understanding of radiative-transfer phenomena and activated N/N₂ chemistry in the Earth's upper atmosphere. Excited states of N₂ are difficult to access experimentally, and analysis of its electric dipole-allowed spectrum is notoriously complex. In this paper, we give an overview of these complexities and of the power of extreme ultraviolet ionization spectroscopy in unraveling many of the observed features. Some illustrative examples from our own research will be discussed.     

碰撞诱导钠分子A1Σ+u→X1Σ+g的荧光光谱

用532.0 nm激光激发Na2分子到B1Πu电子态,记录了Na(3P)原子的跃迁和Na2分子的A1Σ+u-Χ1Σ+g的谱带.由Na与Na2激发态发射的光谱及其强度可以认定在Na-Na2系统中的碰撞过程,Na(3P)原子线是Na2(B1Πu)到Na(3P)的碰撞能量转移产生的,预解离过程也可产生原子线.而A1Σ+u-Χ1Σ+g谱带是由B1Πu到21Σ+g的碰撞转移后再由21Σ+g到A1Σ+u的辐射而引起的.在360℃,根据辐射衰变率和荧光强度,得到Na2(B1Πu)到Na2(21Σ+g)碰撞转移率系数为7.1×10-10 cm3s-1,而B1Πu的预解离率为2.3×106 s-1.     

A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy

A new ³Π-³Σ band was observed in a discharge plasma of the nitrogen molecule and helium using near-infrared diode laser kinetic spectroscopy. All the lines in this band exhibited line broadening of more than 0.1 cm⁻¹. Rotational analysis revealed that the lower state of the transition was the state of N₂, which had already been studied in the D³Σ-E³Σ band. The term value and rotational constant suggested that the upper state is the G³Π_u Rydberg state with an electron configuration of (N₂⁺:X²Σ core)(3pπ_u). The line broadening is attributed to predissociation through a homogeneous interaction with a repulsive Π_u state.     

He2分子b3∏g(v=9)态的预解离

The predissociation of the v=9 level in the b³Π_g state by the c³∑_g⁺ state of helium eximer(He₂) was studied based on the newly observed (9, 3) band in the b³Π_g-a³∑_u⁺ system inthe region of 12065～12445 cm^-1 employing optical heterodyne-concentration modulationabsorption spectroscopy. With the help of the previous potential energy curves and molecular constants of He₂, the corresponding predissociation mechanism for the b³Π_g (v=9) state was analyzed. An RKR potential energy curve of b³Π_g and an ab initio potential curve of c³∑_g⁺ were used to calculate the predissociation linewidths that show basic agreement withobservations, which can quantitatively explain the experiments.     

一氧化二氮的光电离质谱研究

在入射电子能量2500eV、能量分辨200meV的条件下测量了一氧化二氮分子在7.8～24.5 eV的光学振子强度密度谱和光电离质谱,报道了N2O+、NO+、O+、N2+和N+等离子在较高能量分辨下的部分光学振子强度密度,首次给出了一氧化二氮分子在13.0～21.0 eV能区中性解离的振子强度密度.并在对这些数据进行分析的基础上阐述了一氧化二氮分子超激发态的不同退激发道的竞争过程.     

CS2 分子 1 B2(1 Σ+u )态预解离动力学研究

研究了CS2 分子1B2 (1Σ+u )预离解态线形势垒下的g振动能级光解动力学,包括预解离寿命、产物振转布居、平动振动转动能量分配和解离通道分支比.在实验过程中,一束可调谐激光激发超声射流冷却的CS2 分子到1B2 (1Σ+u )电子态,光解产物CS用另一束可调谐激光通过激光诱导荧光(LIF)方法检测.通过拟合光解碎片激发谱的谱峰轮廓,获得了源于不同跃迁初始态的1B2 (1Σ+u )态g振动能级的预解离寿命.通过分析CS的LIF光谱,则获得了不同光解波长下CS碎片的v=0~8振动态布居、v=1、4 ~8振动态的转动布居、能量分配以及两个预解离通道CS(X1Σ+ ) +S(3PJ)和CS(X1Σ+ ) +S(1D2 )的分支比.实验还考察了初始态弯曲振动量子数v2″、振动角动量量子数l对解离动力学的影响.发现v2″的影响不大,而l的影响却是明显的.较大的l(=K)对应于较短的寿命和较小的通道分支比S(3PJ) /S(1D2 ),即大的l(=K)有利于预解离的发生,同时更有利于产生S(1D2 ).     

Predissociation lifetime of the 1σ g 2 2σ g diabatic state of He 2 + : a one-channel approach

Summary This work is concerned with the application of a one-channel model to obtaining predissociation lifetimes and transition rates in a system of crossing diabatic states. The calculation focuses on the first shape resonance of the 1 _g ² 2 _g diabatic state of He ₂ ⁺ , which is relatively stable with respect to tunneling. This resonance predissociates as a result of the 1 _g ² 2 _g state being crossed by the 1 _g 1 _u ² dissociative diabatic state near the resonance level. We have estimated its predissociation lifetime to be of the order of 10^–11 s.     

利用飞秒泵浦探测技术研究碘甲烷B态预解离动力学

应用飞秒双光泵浦-探测技术结合飞行时间质谱研究了碘甲烷分子的B态预解离动力学，其中泵浦光波长为400 nm，探测光为800 nm，碘甲烷主要的产物通道为生成CH3I+和CH3+．改变泵浦与探测光之间的延时，得到了这两种离子的时间演化曲线，每个曲线都可以用两个指数函数来拟合，拟合常数为?1和?2，?1反映了碘甲烷分子吸收三个泵浦激光所到达的高里德堡态的动力学，?2反映了吸收两个泵浦激光所到达的B里德堡态的动力学，得到的B态的带源寿命为1.57 ps，这个值和以前的文献非常符合，试验结果被解释为多光子的电离解     

一氧化二氮的光电离质谱研究

在入射电子能量2500eV、 能量分放200meV的条件 下测量了一氧化二氮分子在7.8-24.5eV的光学振子强度密度谱和光电离质谱,报道了N2O^+、NO^+、O6+、N2^+和N^+等离子在较高能量分辨下的部分光学振 子强度密度,首次给出了一氧化二氮分子在13.0-21.0eV能区中性解离的振子强度密度。并在对这些数据进行分析的基础上阐述了一氧化二氮分子超激发态的不同退激发道的竞争过程。