Theoretical study of the stereodynamics for the reaction F+HBr

The vector correlation between products and reagents for exothermic reaction F + HBr → HF + Br has been studied using a quasi-classical trajectory (QCT) method on the latest extended Lond–Eyring–Polanyi–Sato (LEPS) potential energy surface at three collision energies of 0.1 eV, 0.2 eV and 0.3 eV. Four polarization- dependent generalized differential cross-sections (2π/σ)(dσ₀₀/dω _t ), (2π/σ)(dσ₂₀/dω _t ), (2π/σ)(dσ₂₂₊/dω _t ), (2π/σ)(dσ_21?/dω _t ) have been presented in the centre of mass frame, respectively. The distribution of dihedral angle P(φ _r ), the distribution of angle between k and j ′ , P(θ _r ), are calculated. Both the influence of the collision energy and the influence of the reagent rotation on the product polarization have been studied in the present work, and the results indicate that the product rotational angular momentum j ′ is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The orientation of the HF product rotational angular momentum vector j ′ depends very sensitively on the reagent rotation and also effected by the collision energy.     

基于4A"势能面研究C(3P)+NO(X2Π)→CO(X1Σ+)+N(4S)反应的立体动力学性质

运用准经典轨线方法(QCT), 基于Abrahamsson等构造的⁴A"势能面(Abrahamsson E Andersson S, Nyman G, Markovic N 2008 Phys. Chem. Chem. Phys. 10 4400), 在碰撞能为0.06 eV时, 对C(³P)+NO(X²Π )→CO(X¹Σ⁺)+N(⁴S)反应立体动力学性质进行了理论研究. 在考虑反应物NO转动和振动激发的条件下, 计算了质心坐标系下k-j'矢量(k与j'分别为反应物速度与产物角动量)相关的P(θ_r)分布和k-k'-j'矢量(k'为产物相对速度)相关的P(φ_r)分布. 此外还计算了该反应的三个极化微分截面(2π/σ)(dσ₀₀/dω_t), (2π/σ)(dσ₂₀/dω_t)以及(2π/σ)(dσ₂₂+dω_t). 计算结果表明转动和振动激发对产物取向影响较大而对定向影响较小; 对于三个极化微分截面, 转动激发的影响不大, 而振动激发的影响则较大.     

O (3P) + H2 → OH+H反应的立体动力学研究

用BMS1势能面[Brandão 等, J.Chem.Phys. 121, 8861 (2004)],选取碰撞能为34.6kcal/mol,用准经典轨线方法研究了O ( ) + 反应的立体动力学性质。计算并讨论了k与j'的夹角的分布关系P ( )以及描述k-k'- j'三者关系的二面角分布。（k为反应物速度方向,k'为产物的速度方向,j'为产物的角动量方向） 的峰值在90°附近并且关于90°呈对称性分布,这表明产物角动量的方向与初速度的方向垂直。二面角分布P( )关于散射平面呈反对称性分布,这一结果表明产物的角动量具有强烈的极化效应。另外,我们还研究了振动激发对产物角动量的影响,结果表明产物的矢量性质对反应物的初始振动态非常敏感。     

Theoretical study of the stereodynamics of the He＋HD^＋ reaction

This paper investigates the stereodynamics of the reaction He+HD+ by the quasi-classical trajectory(QCT) method using the most accurate AQUILANTI surface [Aquilanti et al 2000 Mol.Phys.98 1835].The distribution P(φr) of dihedral angle and the distribution P(θr) of angle between k and j have been presented at three different collision energies.Four generalized polarization-dependent differential cross-sections(2π/σ)(dσ00/dωt),(2π/σ)(dσ20/dωt),(2π/σ)(dσ22+/dωt),(2π/σ)(dσ21 /dωt) are also calculated.Some interesting results are obtained from the comparison of the stereodynamics of the title reaction at different collision energies.     

Theoretical study of stereodynamics for the O（3P） ＋ H2 → OH ＋ H reaction

This paper employs the quasi-classical trajectory calculations to study the influence of collision energy on the title reaction on the potential energy surface of the ground ³A' triplet state developed by Rogers et al. (J. Phys. Chem. A 2000 104 2308). It calculates the product angular distribution of P(θ_r), P(φ_r) and P(θ_r, φ_r) which reflects vector correlation. The distribution P(θ_r) shows that product rotational angular momentum vectors j' of the products are strongly aligned along the relative velocity direction k. The distribution of P(φ_r) implies a preference for left-handed product rotation in planes parallel to the scattering plane. Four different polarisation-dependent cross-sections are also presented in the centre-of-mass frame. Results indicate that OH is sensitively affected by collision energies of H₂.     

O~+ + H_2及其同位素取代反应的立体动力学研究

运用准经典轨线方法,基于RODRIGO势能面,对碰撞能为20kcal/mol时,O++H2及其同位素取代反应的立体动力学性质进行了理论研究,对k-j′两矢量相关和k-k′-j′三矢量相关的分布函数、极化微分反应截面,以及产物转动取向参数进行了详细的讨论.结果表明,O++H2→OH++H,O++DH→OD++H和O++TH→OT++H反应的立体动力学性质对体系的质量因数非常敏感.     

Theoretical study of stereodynamics for the N+H2/D2/T2 reactions

The effects of isotopic variants on stereodynamic properties for the title reactions have been investigated using a quasi-classical trajectory method based on the first excited state NH2（I^2A＇） potential energy surface [Li Y Q and Varandas A J C 2010 J. Phys. Chem. A 114 9644]. The forward–backward symmetry scattering of the differential cross section can be observed, which demonstrates that all these reactions follow the insertion mechanism. Three angle distribution functions P（θr）, P（φr）, and P（θr, φr） with different collision energies and target molecules H2/D2/T2 are calculated. It is shown that the product rotational angular momentum is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The title reaction is mainly governed by the ＂in-plane＂ mechanism through the calculated distribution function P（θr, φr）. The observable influences on the rotational polarization of the product by the isotopic substitution of H/D/T can be demonstrated.     

Influence of the reagent vibration on the stereo-dynamics of the reactions D- + H2 and H- + D2

Employing the quasi-classical trajectory method and the potential energy surface of Panda and Sathyamurhy [Panda A N and Sathyamurthy N 2004 J. Chem. Phys. 121 9343], the effect of the reagent vibration on vector correlation of the ion-molecule reactions D^- + H₂ and H^- + D₂ is studied at a collision energy of 35.7 kcal/mol. Four generalized polarization-dependent differential cross sections (2π/σ)(dσ₀₀/dω_t),(2π/σ)(dσ₂₀/dω_t),(2π/σ)(dσ₂₂/dω_t), and (2π/σ)(dσ₂₀/dω_t) are presented in the centre-of-mass reference frame, separately. At the same time, the effects on the product angular distributions P(θ_r), P(φ_r) and P(θ_r,φ_r) of the title reactions are also analysed. The calculated results show that the scattering tendencies of the product HD, the alignment and the orientation of j' sensitively depend on reagent molecule vibration.     

Stereodynamics in reaction O（1D） ＋ CH4 〉OH ＋ CH3

A theoretical study of the stereodynamics for reaction O(1D) + CH4→OH + CH3 has been carried out using the quasiclassical trajectory method(QCT) on a potential energy surface structured by Gonzalez et al. The integral cross sections(ICSs), differential cross sections(DCSs) and product rotational angular momentum polarization have been calculated. With the collision energy increasing, the ICS decreases. There is no threshold energy, because no barrier is found on the minimum energy path. The DCS results show that the backward and forward scatterings exist at the same time. With the collision energy increasing, the dominant rotation of the product changes from the right-handed direction to the left-handed direction in planes parallel to the scattering plane. In the isotopic effect study, the decrease of the mass factor weakens the polarization degree of the rotational angular momentum vectors of the products.     

准经典轨线法研究交换反应H(D)+SH/SD的动力学性质

硫在氢气中的燃烧反应在气象化学、燃烧反应和大气污染中都扮演着重要的角色, 近年来一直受到广泛关注, 其逆反应也渐渐成为人们的研究对象. 以Lü 等得到的精确势能面(Lü S J, Zhang P Y, Han K L, He G Z 2012 J. Chem. Phys. 136 94308) 为基础, 用准经典轨线法对交换反应H(D)+SH/SD的动力学性质进行了研究. 计算了包括反应截面、速率常数、不透明函数、产物振动和转动分布等在内 的标量性质和包括产物散射方向、转动角动量定向和取向性质在内的矢量性质. 详细分析了碰撞能量和同位素效应对反应H(D)+SH/SD 的动力学性质的影响. 结果表明, 随着碰撞能量的增加, 反应截面逐渐增大, 产物的后向散射逐渐减弱, 产物转动角动量的取向和定向性质逐渐增强; 另外, 同位素效应对反应的动力学性质也有明显的影响. 以反应动力学性质和势能面为基础, 详细讨论了反应H(D)+SH/SD 的反应机制. 关键词： 准经典轨线 反应截面 速率常数 振动-转动分布     

Stereodynamics of the O(3P) with H2 (D2) (v=0, j=0) reaction

Quasi-classical trajectory theory is used to study the reaction of O(³P) with H₂ (D₂) based on the ground ³A' potential energy surface (PES). The reaction cross section of the reaction O+H₂ → OH+H is in excellent agreement with the previous result. Vector correlations, product rotational alignment parameters 〈P₂ (j'·k)〉 and several polarized-dependent differential cross sections are further calculated for the reaction. The product polarization distribution exhibits different characteristics that can be ascribed to different motion paths on the PES, arising from various collision energies or mass factors.     

Theoretical study of stereodynamics for the reaction O(3P) +D2 (v=0, j=0) to OD+D and isotope effect

Quasi-classical trajectory (QCT) calculations have been performed to study the product polarization behaviours in the reaction O(³P) + D₂ (v= 0, j= 0)→OD + D. By running trajectories on the ³A′ and ³A″ potential energy surfaces (PESs), vector correlations such as the distributions of the polarization-dependent differential cross sections (PDDCSs), the angular distributions of P(θ_r) and P(ø_r) are presented. Isotope effect is discussed in this work by a comprehensive comparison with the reaction O(³P) + H₂ (v= 0, j= 0) → H + H. Common characteristics as well as differences are discussed in product alignment and orientation for the two reactions. The isotope mass effect differs on the two potential energy surfaces: the isotope mass effect has stronger influence on P(θ_r) and PDDCSs of the ³A′ PES while the opposite on P(ø_r) of the ³A″ potential energy surface.     

反应物振动量子数对O(~1D)+HBr→OH+Br立体动力学影响的研究

采用准经典轨线(QCT)方法计算了O(1D)+HBr→OH+Br反应体系的立体动力学反应.基于由Peterson(J.Chem.Phys.113(2000)4598)等人开发的基态势能面上,计算了反应的矢量相关性质,极角p(θ)r及方位角pφ()r以及空间角pθr,φ()r.此外我们还计算了极化微分反应截面(PDDCSs)的分布各矢量性质随各振动量子数变量的变化.结果表明反应受反应物振动量子数影响较大.     

Stereodynamics of O(3P)+H2 at Scattering Energies of 0.5, 0.75, and 1.0 eV

采用准经典轨线理论,在最低电子势能面1³A”上,对反应在三个不同的散射能量0.5、0.75和1.0 V 进行计算. 介绍了反应物的相对速率矢量k和产物的转动角动量j相关的极角分布,k-k'-j'(k'产物的相对速率矢量) 三矢量相关的方位角和二面角的分布,三维分布,以及与散射角有关的极化微分反应截面.     

反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响

在Peterson的高精度从头计算势能面上,运用准经典轨线方法讨论了反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响.反映两矢量k-j′相关的P(θr)函数的分布说明产物的转动角动量j′在垂直于反应物相对速度矢量k的方向上的排列取向程度随着初始反应物振动量子数的增加而增加;反映三矢量k-k′-j′相关的极角分布函数P(r)显示产物的转动角动量有比较弱的定向效应,且随着初始振动量子数的增加,这种弱的定向效应由沿Y轴负向变为沿Y轴正向.说明反应物分子的初始振动激发有利于增强产物分子的转动排列取向效应,但对产物分子P(r)分布的影响则不明显.     

H/D/T+LiH反应的立体动力学研究

利用准经典轨线方法,在Prudente 等人发表的LiH2体系势能面[Chem. Phys. Lett. 474, 18 (2009)]上研究了原子分子反应H/D/T+LiH →HH/HD/HT+Li的立体动力学性质。在不同碰撞能下分别计算了该反应的反应截面,以及碰撞能为0.25eV时的微分反应截面、角分布P(θr)。计算结果表明,随着碰撞能和攻击原子质量的增加,反应截面逐渐减小。对于所选定的碰撞能,当攻击原子质量增加时,反应产物向前散射趋势增强,向后散射的趋势几乎保持不变,产物的转动角动量j′取向程度增强并且定向于y轴负方向。     

Influence of the reagent vibration on the stereo-dynamics of the reactions D^- ＋ H2 and H^- ＋ D2

Employing the quasi-classical trajectory method and the potential energy surface of Panda and Sathyamurhy [Panda A N and Sathyamurthy N 2004 J.Chem.Phys.121 9343],the effect of the reagent vibration on vector correlation of the ion-molecule reactions D～-+H₂ and H～-+D₂ is studied at a collision energy of 35.7 kcal/mol.Four generalized polarization-dependent differential cross sections （2π/σ）（dσ 00 /dωt）,（2π/σ）（dσ 20 /dωt）,（2π/σ）（dσ 22+ /dωt）,and （2π/σ）（dσ 21 /dωt） are presented in the centre-of-mass reference frame,separately.At the same time,the effects on the product angular distributions P （θr）,P （φr） and P （θr,φr） of the title reactions are also analysed.The calculated results show that the scattering tendencies of the product HD,the alignment and the orientation of j sensitively depend on reagent molecule vibration.     

Quantum stereodynamics study for the reaction F + HD

This paper studies the quantum stereodynamics of the F + HD(υ = 0, j = 0) → HD + F/HF + D reaction at the collision energies of 0.52 and 0.87~kcal/mol. The quantum scattering calculations, based on Stark-Werner potential energy surfaces, show that the differential cross sections for the HF(υ' = 2) + D and DF(υ' = 3) + H channels are consistent with the recent theoretical results. Furthermore, the product rotational angular momentum orientation and alignment have been determined for some selected rovibrational states of the HF + D and DF + H channels.     

Intrinsic product polarization and branch ratio in the S(~1D,~3P)+HD reaction on three electronic states

The intrinsic product polarization and intramolecular isotope effect of the S(~1D,~3P) + HD reaction have been investigated on both the lowest singlet state(1A) and the triplet state(3A and 3A) potential energy surfaces by using quasi-classical trajectory and quantum mechanical methods.The calculations indicate that intramolecular isotope effects are different on the three electronic states.The stereodynamics study shows that the P(θr) distributions,P(φ r) distributions,and polarization-dependent differential cross sections(PDDCSs)(00) are sensitive to mass factor and the product angular momentum vectors are not only aligned but also oriented.     

Quasi-classical Trajectory Study of the Intramolecular Isotope Effect in the Reaction O(3P)+H2/HD

利用准经典轨线方法在BMS1解析势能面上研究了反应O(³P)+H₂体系的动力学性质. 主要研究了同位素效应对该反应体系的积分截面、产物转动态分布、微分截面、产物角动量的取向和定向以及对极化微分截面的影响. 对于微分截面,还考虑了反应物初始振动量子数对微分截面的影响. 对反应O+HD与O+H₂产生OH的转动发布进行比较,发现前者OH的转动激发更为明显. 微分截面的结果表明,振动量子数和同位素对散射方向有一定影响. 同位素取代对产物的取向和定向以及极化微分截面的影响也比较明显. 对以上结果利用已有的理论模型进行了分析,得到了合理的解释.