共查询到20条相似文献,搜索用时 15 毫秒
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首次构造了放热反应Ba+HF(v,J)→BaF(v′,J′)+H的LEPS势能面,并且进行了准经典轨线研究. 对于初始基态,和初始第一激发态的反应物HF,计算得到的BaF产物态分布与实验吻合得比较好. 对产物取向的研究表明,反应体系的质量组合是产物取向的决定因素.反应过程中,直接的提取反应和间接的插入反应是两种竞争的微观反应通道,这种竞争是由于在Ba原子进攻HF分子的时候,即使进攻方向偏离了HF共线的方向也不会引起能垒高度的明显增加.而且低的反应物平动能倾向于提取反应而高的HF振动激发会导致插入反应. 相似文献
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González M Mayneris-Perxachs J Saracibar A Garcia E 《Physical chemistry chemical physics : PCCP》2011,13(30):13638-13644
Rate coefficients for the CH(v = 0,1) + D(2) reaction have been determined for all possible channels (T: 200-1200 K), using the quasiclassical trajectory method and a suitable treatment of the zero point energy. Calculations have also been performed on the CH(v = 1) + H(2) reaction and the CH(v = 1) + D(2) → CH(v = 0) + D(2) process. Most of the results can be understood considering the key role played by the deep minimum of the potential energy surface (PES), the barrierless character of the PES, the energy of the reaction channels, and the kinematics. The good agreement found between theory and experiment for the rate coefficients of the capture process of CH(v = 0) + D(2), the total reactivity of CH(v = 1) + D(2), H(2), as well as the good agreement observed for the related CH(v = 0) + H(2) system (capture and abstraction), gives confidence on the theoretical rate coefficients obtained for the capture processes of CH(v = 1) + D(2), H(2), the individual reactive processes of CH(v = 1) + D(2), H(2), the abstraction and abstraction-exchange reactions for CH(v = 0) + D(2), and the inelastic process mentioned above, for which there are no experimental data available, and that can be useful in combustion chemistry and astrochemistry. 相似文献
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在 QCISD ( T) / / MP2水平下 ,分别采用 6-3 1 1 ++G* * 基组和 SDD基组对重 -轻 -重反应 I+HI(ν=0 )→ IH(ν′=0 ) +I中的 H和 I的偏分势能面进行了 ab initio计算 ,指认出在 0~ 0 .5 8e V碰撞能范围内所产生的 6个散射共振态为 Feshbach共振 ,并与文献报道的量子散射理论计算与高分辨阈值光分离光谱实验结果进行了比较 . 相似文献
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本文用微正则过渡态理论计算了H+O_2(n_0,j_0)→HO+O和C+H_2(n_0, j_0)→CH+H在ab initio势能面上的选态反应截面σ_(n_0,j_0); E.分析了势能面性质对反应截面的影响。计算结果表明, 在指定反应物分子的振动态n_0、转动态j_0时, 两个反应体系的反应截面随相对平动能的增加先是增加后是减小(j_0=1, n_0=0除外); 在给定相对平动能和反应物分子的转动态j_0时, 随反应物分子的振动量子数n_0的增加, 两个体系的选态反应截面均有较显著的增加, 在指定相对平动能和反应物分子的振动态n_0时, H+O_2体系的选态反应截面随j_0的变化较为复杂, 而C+H_2体系则比较简单(j_0=1除外)。对于H+O_2反应体系, 本文得到的反应截面与实验结果及准经典轨迹理论的计算结果符合得很好。 相似文献
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本文运用非含时量子动力学方法研究了H+HF(v=1,j)→H+HF(v'=0,j')传能过程在295~500 K的振动弛豫速率常数.在此温度范围内,所有转动分辨的振动弛豫速率常数随着温度升高而单调递增,速率常数最大的末态转动量子数随着初态转动量子数的增加而增加.在室温下,振动态分辨的振动弛豫速率常数与实验值符合较好.同时,我们也计算了H+HF(v=1,j)→H+HF(v'=1,j')纯转动传能过程在500 K的速率常数,发现它们整体上比振动弛豫速率常数大了几个数量级,并且△j=-1的速率常数一般大于△j=-1的速率常数. 相似文献
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本文用微正则过渡态理论计算了H+O_2(n_0,j_0)→HO+O和C+H_2(n_0,j_0)→CH+H在ab initio势能面上的选态反应截面σ_(n_0,j_0);E.分析了势能面性质对反应截面的影响。计算结果表明,在指定反应物分子的振动态n_0、转动态j_0时,两个反应体系的反应截面随相对平动能的增加先是增加后是减小(j_0=1,n_0=0除外);在给定相对平动能和反应物分子的转动态j_0时,随反应物分子的振动量子数n_0的增加,两个体系的选态反应截面均有较显著的增加,在指定相对平动能和反应物分子的振动态n_0时,H+O_2体系的选态反应截面随j_0的变化较为复杂,而C+H_2体系则比较简单(j_0=1除外).对于H+O_2反应体系,本文得到的反应截面与实验结果及准经典轨迹理论的计算结果符合得很好。 相似文献
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<正>Quasi-classical trajectory(QCT) calculations have been carried out to study the generalized polarization dependent differentialcross sections(PDDCSs) for the reactions H + LiH~+(v = 0,j = 0)→H_2 + Li~+ and H~+ + LiH(v = 0,j = 0)→H_2~+ + Li occurring onthe two lowest-lying electronic states of the LiH_2~+ system,using the ab initio potential energy surfaces(PESs) of Martinazzo et al.[3].Four PDDCSs,i.e.,(2π/σ)(dσ_(00)/dω_t),(2π/σ)(dσ_(20)/dω_t),(2π/σ)(dσ_(22+)/dω_t),(2π/σ)(dσ_(21-)/dω_t) have been discussed in detail. 相似文献
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基于Aguado等人拟合的APW势能面(PES),运用准经典轨线(QCT)方法,对反应Li+HF(v=0,j=0)→LiF+H的动力学性质进行了计算.主要研究了不同碰撞能条件下的反应截面、转动取向、产物散射角分布和竞争反应模式等.结果表明,该反应存在直接提取型和间接插入型两种反应模式,在低能量下反应以间接插入反应模式为主,能量大于200 meV时则以直接提取反应为主. 相似文献
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Quantum scattering LCAC-SW theory studies on reaction probabilities of three-dimensional H+H_2(υ,j)→H_2(υ′, j′)+H reaction 总被引:1,自引:0,他引:1
InlightofKohnvariationtheory,Millerconstructedanewquantumreactivescatteringmethod:theSmatrixvariationmethod[1,2],whichisatypicaloneinwhichalgebraicmethodisusedtosolvedirectlytheSchrdingerequation.Becausethemethodincludesnaturallytheboundaryconditions,thew… 相似文献
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J. Urban V. Klimo V. Staemmler R. Jaquet 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,21(4):329-334
A three-dimensional potential energy surface for the endoergic reaction Ne+H 2 + →NeH++H in the2 A′ ground state of the system NeH 2 + has been calculated by quantum chemical ab initio methods (CEPA approximation). The calculated points on this surface were fitted to an analytic ansatz in terms of an extended LEPS functional form augmented by a correction function. The latter was expanded in polynomials in inverse powers of the internuclear distances. This analytic form was used for quasiclassical trajectory calculations of reactive cross sections. In agreement with experimental investigations a strong vibrational enhancement is observed, i.e. the reaction is markedly favored if the necessary reaction energy is supplied as vibrational energy of H 2 + rather than as relative translational energy. Other properties of the reaction dynamics such as the backward to forward scattering ratio, the lifetime of the collision complex NeH 2 + , and final rotational and vibrational state distributions are also discussed on the basis of the quasiclassical trajectory calculations. 相似文献