Combined iterative diagonalization and statistical sampling in accurate reaction rate calculations: Rotational effects in O+HCl -> OH+Cl
Combined iterative diagonalization and statistical sampling in accurate reaction rate calculations: Rotational effects in O+HCl -> OH+Cl
复制标题
在准确的反应速率计算中结合迭代对角化和统计采样：O HCl -> OH Cl 中的旋转效应
DOI：
10.1063/1.480568
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发表时间：
2000
影响因子：
4.4
通讯作者：
U. Manthe
中科院分区：
文献类型：
--
作者：
Frank Matzkies;U. Manthe
提出了一种改进的统计方法，用于直接计算热速率常数[J. Chem. Phys 110，88（1998）]。在这种方法中，通量相关函数中的轨迹通过迭代对角化（强相互作用）内部自由度和（每周相互作用）旋转自由度中的统计抽样方案进行评估。波包动力学计算采用多组态含时Hartree（MCTDH）方法。研究了O+HCl→OH+Cl反应。这种混合的方法被认为是更有效和更准确的比纯粹的统计方法。在200 ~ 700 K温度范围内详细研究了J位移近似、修正的J位移近似和K守恒近似的精度。
A modification of the statistical approach to the direct calculation of thermal rate constants [J. Chem. Phys 110, 88 (1998)] is presented. Within this approach, the trace in the flux-correlation function is evaluated by iterative diagonalization in the (strongly interacting) internal degrees of freedom and by a statistical sampling scheme in the (weekly interacting) rotational degrees of freedom. The wave packet dynamics is calculated employing the multiconfigurational time-dependent Hartree (MCTDH) approach. The O+HCl→OH+Cl reaction is studied. This mixed approach is found to be more efficient and accurate than the purely statistical approach. The accuracy of the J-shifting approximation, the modified J-shifting approximation, and the K-conserving approximation is investigated in detail between 200 and 700 K.