氯与甲烷和重氢甲烷反应的矢量相关研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面基础上,利用准经典轨线法在碰撞能Ecol=3.67 kcal/mol下研究了Cl+CH4→HCl+CH3和Cl+CD4→DCl+CD3反应,在质心系计算得到四个广义极化微分反应截面((PDDCS)(2π/σ)(dσ00/dωt)、(2π/σ)(dσ20/dωt)、(2π/σ)(dσ22+/dωt)、(2π/σ)(dσ21-/dωt)和k-k′-j′三矢量相关的极角分布p(фr)、k-j′两矢量相关的p(θr)分布以及用θr和фr表示的产物转动角动量的空间分布.计算结果与有关实验及理论结果符合得很好,讨论了氯与甲烷和重氢甲烷反应的立体动力学同位素效应.     

氯与甲烷和重氢甲烷反应的矢量相关研究

在扩展的London?Eyring?Polanyi?Sato(LEPS)势能面基础上,利用准经典轨线法在碰撞能Ecol=3.67 kcal/mol下研究了Cl CH4→HCl CH3和Cl CD4→DCl CD3反应,在质心系计算得到四个广义极化微分反应截面((PDDCS)(2π/σ)(dσ00/dωt)、(2π/σ)(dσ20/dωt)、(2π/σ)(dσ22 /dtω)、(2π/σ)(dσ21-/dωt)和k-k′-j′三矢量相关的极角分布p(r)、k-j′两矢量相关的p(rθ)分布以及用θr和r表示的产物转动角动量的空间分布.计算结果与有关实验及理论结果符合得很好,讨论了氯与甲烷和重氢甲烷反应的立体动力学同位素效应.     

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.     

同位素对Ca+HCl，Ca+DCl，Ca+TCl反应立体动力学性质的影响

基于准经典轨线方法和Verbockhaven等人通过多参考组态相互作用计算建立的势能面研究了Ca+HCl/Ca+DCl/Ca+TCl反应中的矢量相关效应. 计算和分析了 P(θr)和 P(Φr)以及(2π/σ)(dσ₀₀/dω_t), (2π/σ)(dσ₂₀/dω_t), (2π/σ)(dσ₂₂₊/dω_t), (2π/σ)(dσ_21-/dω_{t相似文献}   

Theoretical study of stereodynamics for the D'+ DS(v=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 3 A 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(θr), P(φr), and P(θr,φr), together with the four commonly used polarization-dependent differential cross sections ((2π/σ)(dσ00/dωt), (2π/σ)(dσ20/dωt), (2π/σ)(dσ22+/dωt), (2π/σ)(dσ21/dωt)) 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.     

氯与甲烷和重氢甲烷反应的矢量相关研究

在扩展的London Eyring Polanyi Sato（LEPS）势能面基础上，利用准经典轨践法在碰撞能Ecd=3．67 kcal／mol下研究了Cl＋CH4→HCl＋CH3和Cl＋CD4→DCl＋CD3反应，在质心系计算得到四个广义极化微分反应截面（（PDDCS）（2π／σ）（dσ00／dωt）、（2π／σ）（dσ20/dωt）、（2π／σ）（dσ22／dωt）、（2π／σ）（dσ21／dωt）和k—k’- j’三矢量相关的极角分布P（φr）、k—j’两矢量相关的P（θr）分布以及用以和丸表示的产物转动角动量的空间分布．计算结果与有关实验反理论结果符合得很好，讨论了氯与甲烷和重氢甲烷反应的立体动力学同位素效应。     

The collision energy effect on the stereodynamics of the Ca + HCl→CaCl + H reaction

The stereodynamics of the reaction of Ca + HCl are calculated at three different collision energies based on the potential energy surface [Verbockhaven G et al. 2005 J. Chem. Phys. 122 204307] using quasi-classical trajectory theory. The polarization-dependent differential cross sections (PDDCSs) (2π/σ )(dσ 00 /dω t ), (2π/σ )(dσ 20 /dωt ), (2π/σ )(dσ 22+ /dωt ), (2π/σ )(dσ 21 /dω t ) and the distributions of P(θ r ), P(φr ), and P(θr ,φr ) are calculated. The results indicate that the rotational polarization of the CaCl product presents different characteristics for the different collision energies, and the effects of the collision energy on the vector potential, including the alignment, orientation, and PDDCSs, are not obvious.     

Quasi-classical trajectory study of collision energy effect on the stereodynamics of H + Br O → O + HBr reaction

Quasi-classical trajectory(QCT) studies on the stereodynamics of H + Br O → O + HBr reaction have been performed on the X1A′state of ab initio potential energy surface by Peterson [Peterson K A 2000 J. Chem. Phys. 113 4598] in a collision energy range from 0 kcal/mol to 6 kcal/mol. Two of the polarization-dependent generalized differential cross sections(PDDCSs),(2π /σ)( dσ00/ dωt)(PDDCS00) and(2π /σ)( dσ20/ dωt)(PDDCS20) are considered. The rotational polarizations of these products show sensitive behaviors to the calculated collision energy range. Furthermore, in order to gain more knowledge about vector correlations, the product angular distribution, P(θr), and the dihedral angle, P(φr),are calculated, and the results indicate that both the rotational alignment and orientation of the product are enhanced as collision energy increases.     

Cl与C3D6H2和C3H6D2反应的立体动力学对比研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面上,利用准经典轨线法研究了碰撞能为Ecol=6.0 kcal/mol时Cl与C3D6H2和C3H6D2反应.在质心系中计算了极化微分反应截面(2π/σ)(dσ00/dtω)、两矢量相关的P(rθ)分布、三矢量相关的极角分布P(Φr)以及用θr和r表示的产物转动角动量的空间分布,计算结果与有关实验及理论结果符合得很好.通过对比研究Cl与C3D6H2、C3H6D2和C3H8在不同碳位上的反应,发现质量因子在此类反应中起着重要的作用.     

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.     

C1与C3D6H2和C3H6D2反应的立体动力学对比研究

在扩展的London-Eyring-Polanyi-Sato（LEPS）势能面上，利用准经典轨线法研究了碰撞能为Ecol=6．0kcal／mol时C1与C3D6H2和C3H6D2反应．在质心系中计算了极化微分反应截（2π／σ）（dσ00／dωt）、两矢量相关的P（θr）分布、三矢量相关的极角分布P（Ф）以及用θr和Фr表示的产物转动角动量的空间分布，计算结果与有关实验及理论结果符合得很好．通过对比研究C1与C3D6H2、C3H6功和C3H8在不同碳位上的反应，发现质量因子在此类反应中起着重要的作用．     

振动激发对H+CH反应矢量性质的影响

基于从头算势能面CH2(1A'),用准经典轨线(QCT)方法研究了不同振动激发(v=0-3)下反应H+CH→H2+C(1D)的动力学性质.在质心坐标系下计算了四个极化微分反应截面(PDDCDs),计算并讨论了描述k-j'矢量相关的P(θr)分布函数和描述k-k-'j'三矢量相关的二面角分布P(φr).研究结果表明势能面上的深势阱和不同的振动态对产物分子H2有重要影响.     

Stereodynamics of the reactions Ne+H₂⁺/Ne+D₂⁺/Ne+T₂

The vector correlations between products and reagents for the reactions Ne+H + 2 , Ne+D + 2 , and Ne+T + 2 are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lü et al. [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections (2π/σ)(dσ 00 /dω t ), (2π/σ)(dσ 20 /dω t ), (2π/σ)(dσ 22+ /dω t ), and (2π/σ)(dσ 21 /dω t ), and the distributions of P (θ r ), P (φ r ), and P (θ r ,φ r ) are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Stereodynamics of the reactions Ne+H2+/Ne+D2+/Ne+T2

The vector correlations between products and reagents for the reactions Ne+H + 2 , Ne+D + 2 , and Ne+T + 2 are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lü et al. [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections (2π/σ)(dσ 00 /dω t ), (2π/σ)(dσ 20 /dω t ), (2π/σ)(dσ 22+ /dω t ), and (2π/σ)(dσ 21 /dω t ), and the distributions of P (θ r ), P (φ r ), and P (θ r ,φ r ) are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Ca+RBr→CaBr+R(R=CH3,C2H5,n-C3H7)反应的矢量相关和产物的转动取向

采用准经典轨线方法研究了碰撞反应 Ca RBr(R=CH_3,C_2H_5 和 n-C_3H_7)的矢量相关性质和产物 CaBr 分子的转动取向.计算了不同碰量相关撞能情况下产物分子的转动取向参数和反应物与产物之间的矢分布几率函数.矢量相关由角分布函数 P(θ_r)!P(φ_r)和 P(θ_r,φ_r)以及极化相关微分截面来描述.Ca CH_3Br 反应产物 CaBr 的 P(θ_r)峰值大于 Ca C_2H_5Br 和 Ca n-C_3H_7Br 反应产物 CaBr 的 P(θ_r)峰值.对于反应 Ca RBr 的 P(θ_r)在φ_=3π/2处的峰值明显大于φ_r=π/2处的峰值.计算结果表明,在碰撞反应过程中,产物 CaBr 分子的转动角动量不仅发生取向,而且沿着垂直于散射面方向发生定向：产物 CaBr 分子强烈地沿着反应物相对速度方向向前散射；产物分子转动角动量的定向和取向将不同程度地影响产物的散射方向.     

Stereodynamics of the reactions Ne＋H＋/Ne＋D2＋/Ne＋W2

The vector correlations between products and reagents for the reactions Ne＋H2＋, Ne＋D2＋, and Ne＋T2＋ are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lfi et al, [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections （27π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dwt）, （27π/σ）（dσ22＋/dwt）, and （2π/σ）（dσ21-/dwt）, and the distributions of P（θr）, P（φ）, and P（θr, Cr） are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Effect of isotope on state-to-state dynamics for reactive collision reactions ■ and ■ in ground state 1~2 A’’ and first excited 1~2 A’ potential energy surfaces

We carry out quantum scattering dynamics and quasi-classical trajectory(QCT) calculations for the O+H_2~+ reactive collision in the ground(1~2 A").nd first excited(1~2 A') potential energy surface.We calculate the reaction probabilities of O+H_2~+(v=0,j=0)→OH~++H and O+H_2~+(v=0,j=0)→OH+H~+reaction for total angular momentum J=0.The results calculated by QCT are consistent with those from quantum mechanical wave packet.Using the QCT method,we generate in the center-of-mass frame the product state-resolved integral cross-sections(ICSs);two commonly used generalized polarization-dependent differential cross-sections(PDDCS s),(2π/σ)(dσ_(00)/dω_t),(2π/σ)(dσ_(20)/dω_t));and three angular distributions of the product rotational vectors,p(θ_r),P(φ_r),and p(θ_r,φ_r).We discuss the influence on the scalar and vector properties of the potential energy surface,the collision energy,and the isotope mass.Since there are deep potential wells in these two potential energy surfaces,their kinetic characteristics are similar to each other and the isotopic effect is not obvious.However,the well depths and configurations of the two potential energy surfaces are different,so the effects of isotopic substitution on the integral cross-section and the rotational polarization of product are different.     

反应物NO的振动激发对反应C(3P)+NO(X2Π)→CO(X1Σ+)+N(2D)立体动力学性质的影响

采用准经典轨线方法研究碰撞能为0.23 eV时,反应物分子NO在不同初始振动态(v=0～3)下发生在两个电子态(2A″和2A′)势能面上反应C(3P)+NO(X2Π)→CO(X1Σ+)+N(2D)的立体动力学性质.计算反应产物的转动角动量矢量分布(P(θr)和P(?r))以及微分散射截面(P00(ωt),(P)20(ω...     

碰撞能对H+HS交换反应立体动力学性质的影响

基于从头算的对称性为1A'的势能面,利用准经典轨线(QCT)方法在不同的碰撞能下研究了交换反应H+HS→HS+H的产物和反应物的矢量相关性质.在质心坐标系下分别计算了反应的描述k-j'矢量相关的P(θr)分布和描述k-k'-j'三者矢量相关的P(φr)分布.同时我们还计算了反应产物的四个极化微分截面.计算结果表明势阱和碰撞能对该反应产物的矢量相关具有重要影响.     

碰撞能对O++DH (v=0, j=0)→OD++H的准经典轨线

运用准经典轨线的方法,基于RODRIGO势能面,研究反应体系O⁺+DH (v=0, j=0)→OD⁺+H的立体动力学性质. 对描述k-j′两矢量相关和k-k′-j′三矢量相关的分布函数P(θr)和P(φr)以及产物转动取向参数进行了详细的讨论,发现极化微分反应截面呈现有趣的现象. 计算了反应几率与反应截面. O⁺+DH (v=0, j=0)→OD⁺+H反应的立体动力学性质对体系的碰撞能非常敏感.