A new time‐dependent approach to the direct calculation of reaction rates
A new time‐dependent approach to the direct calculation of reaction rates
复制标题
直接计算反应速率的新的时间相关方法
DOI：
10.1063/1.468870
复制
发表时间：
1995
影响因子：
4.4
通讯作者：
U. Manthe
中科院分区：
文献类型：
--
作者：
U. Manthe
本文提出了一种直接计算化学反应速率常数的波包动力学方法。基于米勒、施瓦茨和特龙普[J. Chem. Phys. 79，4889（1983）]的位置-通量相关函数，引入了一个反应速率算符，它可以被看作是能量依赖的反应概率算符[J. Chem. Phys. 99，3411（1993）]的热模拟。结果表明，该反应速率算符一般只有少数本征值不为零的本征态。这些本征态可以被解释为振动基态和振动激发态的活化复合物。本征态和本征值可以有效地计算通过迭代（Lanczos）对角化方案。所需的波包传播的数量大约等于激活的复合物的相关状态的数量，它是相当小的，因为在以前的方法来计算基于波包动力学的速率常数。新...
A wave packet dynamical approach to the direct calculation of the rate constant of a chemical reaction is presented. Based on the position‐flux correlation function of Miller, Schwartz, and Tromp [J. Chem. Phys. 79, 4889 (1983)] a reaction rate operator is introduced, which can be viewed as the thermal analog of the energy‐dependent reaction probability operator [J. Chem. Phys. 99, 3411 (1993)]. It is shown that this reaction rate operator has in general only a small number of eigenstates with nonvanishing eigenvalues. These eigenstates can be interpreted as the vibrational ground state and the vibrationally excited states of the activated complex. The eigenstates and eigenvalues can efficiently be computed via an iterative (Lanczos) diagonalization scheme. The number of wave packet propagations required equals approximately the number of relevant states of the activated complex, it is considerably smaller as in previous approaches to the calculation of rate constants based on wave packet dynamics. The ne...