González Javier, Giménez Xavier, Bofill Josep Maria
Institut de Química Avançada de Catalunya, Consejo Superior de Investigaciones Científicas, Jordi Girona 18, 08034 Barcelona, Spain.
J Chem Phys. 2009 Aug 7;131(5):054108. doi: 10.1063/1.3194135.
A derivation of a quantum reaction path Hamiltonian is proposed, which is based on a reformulation of the classical version of Gonzalez et al. [J. Phys. Chem. A 105, 5022 (2001)], and the resulting equations are solved by means of a discrete variable representation approach, leading to a well-suited algorithm for the calculation of quantum dynamics of chemical reactions involving polyatomic molecules. General expressions for any type of reaction path are presented with special interest in the intrinsic reaction coordinate, which have been used to study selected cases, including a one-dimensional Eckart barrier, for which results are shown to be exact, two bidimensional systems, namely, a Muller-Brown potential energy surface, which is characteristic of polyatomic isomerization processes, and the collinear H + H(2) chemical reaction, and finally the tridimensional, J = 0, F + H(2) reaction. Results for the specific chemical systems are shown to be in quite good agreement with exact two- and three-dimensional quantum calculations concerning autocorrelation functions as well as transmission factors as a function of total energy.
提出了一种量子反应路径哈密顿量的推导方法，该方法基于对冈萨雷斯等人经典版本[《物理化学杂志A》105, 5022 (2001)]的重新表述，并通过离散变量表示方法求解所得方程，从而得到一种非常适合计算涉及多原子分子化学反应量子动力学的算法。给出了任何类型反应路径的通用表达式，特别关注内禀反应坐标，这些表达式已用于研究特定案例，包括一维埃卡特势垒（其结果显示是精确的）、两个二维系统，即多原子异构化过程所特有的穆勒 - 布朗势能面以及共线H + H(2)化学反应，最后是三维J = 0的F + H(2)反应。特定化学系统的结果显示与关于自相关函数以及作为总能量函数的透射因子的精确二维和三维量子计算结果相当吻合。
