利用双光缔合光谱技术直接测量超冷铯分子0u+(6S1/2+6P1/2)长程态的转动常数的实验研究

实验获得了超冷铯分子6S_1/2+6P_1/2离解限下0_u⁺长程态振动能级v=187的转动常数. 首先利用调制的荧光光谱技术获得了高分辨的转动量子数J=0–6的超冷铯分子纯转动光谱. 利用双光缔合光谱技术, 构建了高精度的频率参考信号, 进而得到了相邻转动能级间的频率间隔. 最后通过非刚性转子模型拟合得到了转动常数和离心畸变常数.     

O(3P)+CD4反应的含时波包动力学计算

基于Modified Jordan和Gilbert的势能面,运用SVRT(semirigid vibrating rotor target)模型和TDWP(Time-Dependent Wave Packet)方法,对O(3P)+CD4反应体系进行了含时量子动力学计算,给出了该体系的总反应几率,散射截面和热速率常数等结果.通过对j=0时, v=0,1的反应几率的计算,看出D-CD3的振动激发,极大地提高了反应几率,而反应阈能明显降低,说明反应分子的振动能对分子的碰撞反应有重要贡献. 而对于v=0时j=0,1,2,3的反应几率的计算,得出转动量子数j的增大,也会使反应几率有较大的提高,但反应阈能基本不变.     

O(3P)+CD4反应的含时波包动力学计算

基于Modified Jordan和Gilbert的势能面,运用SVRT(semirigid vibrating rotor target)模型和TDWP(Time-Dependent Wave Packet)方法,对O(3P)+CD4反应体系进行了含时量子动力学计算,给出了该体系的总反应几率,散射截面和热速率常数等结果.通过对j=0时, v=0,1的反应几率的计算,看出D-CD3的振动激发,极大地提高了反应几率,而反应阈能明显降低,说明反应分子的振动能对分子的碰撞反应有重要贡献. 而对于v=0时j=0,1,2,3的反应几率的计算,得出转动量子数j的增大,也会使反应几率有较大的提高,但反应阈能基本不变.     

D+CD4→CD3+D2反应的四维量子散射计算

运用约化维数量子动力学理论，利用含时波包法，对反应D+CD₄→CD_{3+D2进行了四维量子散射计算.将反应多原子CD4看作双原子D—CD 3，反应D+CD4→CD3+D2看作单原子-双原 子反应，把体系的反应简化为四维散射问题. 波函数的传播采用分裂算符法，为避免格点边界处含时波函数的边界反射，采用了光学吸收 势法，在格点边界处引入光学势，消除边界反射.根据CD4分子的C3v对称性， 选取了Jordan和Gilbert提出的半经验势能面.计算结果表明，反应概率随平动能的变化图像 ，呈现出显著的量子共振特性，这是很多提取反应的共同特征.而不同振动态下的反应概率 随平动能的变化表明，随振动量子数的增大，反应概率有明显提高，且反应阈能明显降低， 这说明反应分子的振动能对分子的碰撞反应有重要贡献.而对基态和第一振动激发态时散射 截面的计算，也证明了这一结论.同时，还分别通过计算量子数j，k，m对反应概率的影响， 对该反应的空间取向效应进行了研究，并与H+CH4→CH3+H2反应进行了比较. 关键词： 含时波包 量子散射 反应概率}     

SiCl自由基X2Π和A2Σ+态的光谱性质

采用内收缩多参考组态相互作用(ic MRCI)方法结合Dunning等相关一致基,计算Si Cl自由基X²Π和A²Σ⁺态的势能曲线.讨论参考能和相关能外推对X²Π和A²Σ⁺态光谱的影响.对势能进行相对论修正及核价修正计算.拟合势能曲线得到X²Π和A²Σ⁺态的光谱常数.它们与实验结果一致.利用Breit-Pauli算符,计算旋轨耦合效应,得到X²Π_1/2和X²Π_3/2的势能曲线、并计算它们的光谱常数.求解双原子分子核运动的径向SchrÖdinger方程,获得无转动SiCl自由基2个Λ-S态及X²Π态的耦合分裂态的全部振动态.得到J=0时X²Π态的自旋-轨道耦合常数、较高振动态的惯性转动常数以及X²Π_1/2和X²Π_3/2的振动能级等分子常数.     

D+DBr反应的态-态动力学研究

在0—2.0 eV的碰撞能范围内采用含时量子波包方法和二阶分裂算符传播子对初始量子态为(v_0=0,j_0=0)的D+DBr反应进行了态分辨理论水平上的动力学计算.计算了抽取反应通道D+DBr→Br+D_2和置换反应通道D'+DBr→D+D'Br的反应概率、积分截面、微分截面、产物的振动和转动分布以及速率常数等动力学性质,并与相应的理论和实验结果进行了比较.结果表明:计算的速率常数与实验结果十分符合.微分截面的结果表明:对于抽取反应,前向的剥离反应机制在反应过程中占据主导地位;对于置换反应,头碰头的反弹机制占据主导地位.     

SF分子基态及低激发态势能函数与光谱常数的研究

采用含Davidson修正的内收缩多参考组态相互作用的方法和考虑相对论修正, 在价态范围内的最大相关一致基 aug-cc-pV6Z 的条件下, 对SF分子的基态²∏及几个低激发态⁴∑^-, ²∑^-, ²Δ进行了势能扫描计算. 对SF分子的势能曲线进行拟合, 得到了该分子的光谱常数R_e, ω_e, ω_eχ_e, D₀, D_e, B_e和 α_e, 通过比较发现它们与已有的实验结果较为一致. 利用SF分子的势能曲线, 通过求解双原子分子核运动的径向Schrödinger方程得到J=0 时SF分子所计算各电子态的多个振动态. 对于每一振动态, 分别计算了振动能级、惯性转动常数和离心畸变常数. 关键词： SF 势能曲线 光谱常数 分子常数     

有机溶液中圆锥泡声致发光

在U形管声致发光装置的基础上建立了一套新型的声致发光装置——直管圆锥泡声致发光装置. 利用此装置以有机溶液为液体介质得到了超强的发光脉冲并测量得到了其发光光谱. 结果表明发光光谱为一从紫外光至可见光波长范围的连续谱,上面叠加有C₂的d³Π_g→d³Π_u跃迁形成的五个序列谱带,分别对应于Δv=-2,Δv=-1,Δv=0,Δv< 关键词： 声致发光 光谱 斯旺带 振动温度     

虚阴极产生微波的一些基本特性

用Vlasov-Poisson方程对相对论电子束在单板、双板间的传播过程进行了数值模拟,给出了单板模型空间电荷积累最大的位置,不同位置上的电流J、电子数密度n、电场E的振荡频率随入射电子数密度n₀、入射速度v₀的变化关系,双板模型空间电荷积累最大的位置,J、n、E的振荡频率随入射流J₀及两板间距离的变化关系。虚阴极位置的数值结果与稳态理论给出的结果相近,它的振荡频率符合经验公式(1~√2π)ω_peb。单板时入射电子数密度按速度服从高斯分布,能散△E_n/E_n < 10%时的数值结果给出与单能情况基本相同的结论。     

基于三级Fabry-Perot标准具的纯转动拉曼测温激光雷达

提出了新的纯转动拉曼测温雷达系统,即以种子激光注入锁定的Nd:YAG激光器为激发光源,采用基于三级Fabry-Perot(F-P)标准具的双通道分光结构代替双光栅单色仪结构.通过通道中宽带滤光片(带宽为7nm)及F-P标准具的组合使用,对532nm激发光的大气Mie-Rayleigh弹性回波散射抑制比可达10^-10,对量子数J=±6,J=±12的N₂纯转动拉曼散射光谱线接收带宽均小于10pm,因此能充分抑制大气背景辐射噪声及O₂纯转动拉曼谱线的干扰,从而实现了单谱线比反演温度,提高了探测精度,且可在白昼探测大气对流层温度.最后通过探空气球测得的对流层温度垂直分布逆向模拟了该系统双通道的Raman信号曲线,证实了该系统的可行性. 关键词： 拉曼激光雷达 纯转动拉曼散射 三级Fabry-Perot标准具 对流层     

Exact quantum dynamics study of the H(2S)+SiH+(X1Σ+) reaction on a new potential energy surface of SiH2+(X2A1)

Based on a new global potential energy surface of SiH₂⁺(X²A₁), the exact quantum dynamical calculation for the H(²S)+SiH⁺(X¹Σ⁺)→H₂+Si⁺ reaction has been carried out by using the Chebyshev wave packet method. The initial state specified (ν_i=0, j_i=0) probabilities, integral cross sections (ICS) and thermal rate constants of the title reaction are calculated. All partial wave contributions up to J=90 are calculated in exact quantum calculation including the full Coriolis coupling (CC) effect. The dynamical behaviors of probabilities, ICSs and rate constants are found to be in accord with an exothermic reaction without potential barrier. By comparing the probabilities of CC with the corresponding centrifugal sudden (CS) approximation ones, it can be concluded that neglecting CC effect will decrease the collision time, increase the amplitude of oscillation and lead to overestimation or underestimation of the reaction probability. For ICSs and rate constants, it is found that the deviation of CC and CS ICSs is small in the most of collision energy range except for the range of 0 eV-0.05 eV, while the deviation of both rate constants is considerable in the temperature range of 16 K-1000 K.     

Theoretical study of stereodynamics for the D'+DS(ν = 0,j = 0)→D'D+S abstraction reaction

Quasiclassical trajectory (QCT) calculations have been performed for the abstraction reaction, D' +DS(v = 0, j = 0)→D'D+S on a new LZHH potential energy surface (PES) of the adiabatic 3A' electronic state [Lü et al. 2012 J. Chem. Phys. 136 094308]. The collision energy effect on the integral cross section and product polarization are studied over a wide collision energy range from 0.1 to 2.0 eV. The cross sections calculated by the QCT procedure are in good accordance with previous quantum wave packet results. The three angular distribution functions, P(θ_r), P(φ_r), and P(θ_r,φ_r), together with the four commonly used polarization-dependent differential cross sections ((2π/σ)(ds₀₀/dω_t), (2π/σ)(ds₂₀/dω_t), (2π/σ)(ds₂₂₊/dω_t), (2π/σ)(ds_21-/dω_t)) are obtained to gain insight into the chemical stereodynamics of the title reaction. Influences of the collision energy on the product polarization are exhibited and discussed.     

采用量子波包方法和准经典轨线方法研究S(~3P)+HD反应

利用量子波包方法和准经典轨线方法在一个新的3A′′势能面上研究了S(3P)+HD→SD+H和SH+D反应的动力学性质.计算得到了两个反应通道在碰撞能为0.8—2.2 eV范围内的J=0反应几率、积分反应截面、内同位素因子和产物转动取向因子.这些结果揭示了S(3P)+HD反应非常明显的内同位素效应.通过对势能面和反应轨线的分析,我们发现了SD+H反应通道一个新的反应机制.S(3P)+HD反应的内同位素效应可以利用新发现的反应机制和反应的质量组合来进行解释.     

0.5 eV时H++D2(v=0,j=0) 反应的微分、积分截面

基于ab initio势能面(KBNN PES)[1],用耦合通道超球坐标理论研究了碰撞能等于0.5 eV时H D2(v=0,j=0)的积分,微分截面.对于反应性碰撞,计算的积分截面表明由于深势阱的存在使得这一绝热反应产物的分布表现出一种近似的统计行为.计算的微分截面反映该体系存在着长寿命的中间络合物;对于非反应性碰撞(传能过程),平动—平动传能过程更有效,且其积分截面随着转动量子数的增大而显著减少.通过反应性碰撞和非反应性碰撞积分截面的比较,发现在低能碰撞情况,非反应性碰撞更容易进行.     

基于新CH2(X-3A″)势能面的C(3P)+H2(X1∑g^+)→H(2S)+CH(2Π)反应量子波包动力学

基于一个最新的CH2(X-3A″)势能面,运用切比雪夫波包方法对初始态为(v=0,j=0)的C(3P)+H2(X1∑g^+)→H(2S)+CH(2Π)反应体系在1.0-2.0 eV的碰撞能量范围内进行了动力学研究.通过对角动量量子数J=60以下的所有分波进行计算,得到了反应几率、积分散射截面和速率常数.计算中用到了耦合态近似方法和考虑科里奥利耦合效应的精确量子方法.通过对比发现,随着角动量量子数以及能量的增加,科里奥利耦合效应的影响越发显著,因而对于该反应体系,科里奥利耦合效应不可忽略.本文计算所得的积分散射截面和速率常数尚无实验数据可以比较,对该反应的后续研究有一定的参考价值.     

Effects of collision energy and rotational quantum number on stereodynamics of the reactions:H(~2S)+NH(v=0,j=0,2,5,10)→N(~4S)+H_2

The stereodynamical properties of H(~2S) + NH(v = 0,j = 0,2,5,10)→N(~4S) + H_2 reactions are studied in this paper by using the quasi-classical trajectory(QCT) method with different collision energies on the double many-body expansion(DMBE) potential energy surface(PES)(Poveda L A and Varandas A J C 2005 Phys.Chem.Chem.Phys.7 2867).In a range of collision energy from 2 to 20 kcal/mol,the vibrational rotational quantum numbers of the NH molecules are specifically investigated on v = 0 and j = 0,2,5,10 respectively.The distributions of P(θ_r),P(φ_r),P(θ_r,φ_r),(2π/σ)(dσ_(00)/dω_t)differential cross-section(DCSs) and integral cross-sections(ICSs) are calculated.The ICSs,computed for collision energies from 2 kcal/mol to 20 kcal/mol,for the ground state are in good agreement with the cited data.The results show that the reagent rotational quantum number and initial collision energy both have a significant effect on the distributions of the k-j',the k-k'-j',and the k-k' correlations.In addition,the DCS is found to be susceptible to collision energy,but it is not significantly affected by the rotational excitation of reagent.     

使用态-态分辨的量子波包方法对Li+HF/DF反应的研究

使用基于反应物坐标的含时量子波包方法,在APW势能面上,计算了碰撞能在0～0.25 eV范围的Li+HF/DF(v=0,j=0,1)反应的积分和微分截面．同时也计算了初始态选择的反应速率常数．计算结果表明,Li+DF和Li+HF反应产物分布基本类似,只是前者产物转动激发态稍微多些．反应物的转动激发对于Li+DF反应影响很小．这两个反应的微分截面都是前向散射为主的,特别是在碰撞能较高时候．产物振转态分辨的积分截面和后向散射随碰撞能而呈现的振荡现象,可以用来指认Li+HF反应中的共振态．Li+HF的反应速率常数在100～300 K几乎不变,而Li+DF的反应速率常数则增长了10倍左右．Li+HF的反应几率和积分截面和以前报道的结果总体符合较好,差别应该是计算收敛性更好所致．     

Quantum dynamics study of isotope effects of the OD/OH + CH3 reactions

ABSTRACT

A six-degrees-of-freedom, time-dependent quantum dynamics calculation is employed to study the integral cross sections, full-dimensional cumulative reaction probabilities and full-dimensional rate constants for the isotopic reactions of the OD and OH with CH₃ reactions. The full-dimensional cumulative reaction probabilities and full-dimensional rate constants are obtained using the energy and J-K shifting approaches based on the six-degrees-of-freedom calculations. The comparison of integral cross sections shows that the OD?+?CH₃ reaction has a larger energy threshold and a smaller tunnelling effect than the OH?+?CH₃ reaction. The corrected rate constants using the experimental zero-point energy have a very good agreement with the experimental results. The comparison of the rate constants shows that the OD?+?CH₃ has smaller rate constants than the OH?+?CH₃ reaction, which indicates a smaller reactivity due to the isotope substitution.     

Time-dependent quantum wave packet and quasiclassical trajectory studies of the Au(2S) + H2(X1∑+g) → AuH(X1∑+g) + H(2S) reaction

The time-dependent quantum wave packet (TDWP) and quasiclassical trajectory calculations (QCT) are carried out for the Au(²S) + H₂(X¹∑⁺_g) → AuH(X¹∑⁺_g) + H(²S) reaction on a global potential energy surface. The reaction probabilities at a series of J values, integral cross sections (ICSs) and differential cross sections of the title reaction are calculated by the TDWP method. For reaction probabilities, there are a mass of sharp oscillations at low collision energy, which can be attributed to resonances supported by the potential well. Due to the endothermicity of the title reaction, the total ICS shows a threshold about 1.53 eV. In order to further investigate the reactive mechanism, the lifetime of complex is calculated by QCT method. At the low collision energy, most intermediate complexes are long lived, which implies that the reaction is governed by indirect reactive mechanism. With the collision energy increasing, the direct reactive mechanism occupies the dominant position. Due to the change of the reactive mechanism, the angular distribution shifts toward the forward direction with collision energy increasing. The isotopic variant, Au + D₂→AuD + D reaction, is also calculated by TDWP method. The calculated reaction probabilities and ICSs show that the isotope effect reduces the reactivity.     

The stereodynamic properties of the F + HO (v,j)→HF + O reaction on the 1A' and 3A' potential energy surfaces by quasi-classical trajectory: Initial excitation effect (v =1-3, j = 0 and v = 0, j =1-3)

The stereodynamic properties of the F + HO (v, j) reaction are explored by quasi-classical trajectory (QCT) calculations performed on the ¹A' and ³A' potential energy surfaces (PESs). Based on the polarization-dependent differential cross sections (PDDCSs) and the angular distributions of the product angular momentum with the reactant at different values of initial v or j, the results show that the product scattering and product polarization have strong links with initial vibrational-rotational numbers of v and j. The significant manifestation of the normal DCSs is that the forward scattering gradually becomes predominant with the initial vibrational excitation increasing, and the scattering angle of the HF product taking place on the ³A' potential energy surface is found to be more sensitive to the initial value of v. The product orientation and alignment are strongly dependent on the initial rovibrational excitation effect. With enhancement in the initial rovibrational excitation effect, there is an overall decrease in the product orientation as well as in the product alignment either perpendicular to the reagent relative velocity vector k or along the direction of the y axis, for which the initial rotational excitation effect is much more noticeable than the vibrational excitation effect. Moreover, the initial rovibrational excitation effect on the product polarization is more pronounced for the ³A' potential energy surface than for the ¹A' potential energy surface.