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Bifurcations of dividing surfaces in chemical reactions

机译:化学反应中分割面的分叉

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We study the dynamical behavior of the unstable periodic orbit (NHIM) associated to the non-return transition state (TS) of the H_2 H collinear exchange reaction and their effects on the reaction probability. By means of the normal form of the Hamiltonian in the vicinity of the phase space saddle point, we obtain explicit expressions of the dynamical structures that rule the reaction. Taking advantage of the straightforward identification of the TS in normal form coordinates, we calculate the reaction probability as a function of the system energy in a more efficient way than the standard Monte Carlo method. The reaction probability values computed by both methods are not in agreement for high energies. We study by numerical continuation the bifurcations experienced by the NHIM as the energy increases. We find that the occurrence of new periodic orbits emanated from these bifurcations prevents the existence of a unique non-return TS, so that for high energies, the transition state theory cannot be longer applied to calculate the reaction probability.
机译:我们研究了与H_2H共线交换反应的单向过渡态(TS)相关的不稳定周期轨道(NHIM)的动力学行为及其对反应概率的影响。通过在相空间鞍点附近的哈密顿量的范式,我们获得了控制反应的动力学结构的明确表示。利用标准形式坐标中TS的直接识别优势,我们以比标准Monte Carlo方法更有效的方式来计算反应概率与系统能量的关系。通过两种方法计算出的反应概率值与高能量不一致。我们通过数值连续性研究随着能量增加,NHIM所经历的分叉。我们发现,从这些分叉发出的新的周期性轨道的出现阻止了独特的止回TS的存在,因此对于高能,过渡态理论不能再用于计算反应概率。

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