Cvitas Marko T, Althorpe Stuart C
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, U.K.
J Phys Chem A. 2009 Apr 23;113(16):4557-69. doi: 10.1021/jp8111974.
We describe a quantum wave packet method for computing the state-to-state quantum dynamics of 4-atom AB + CD --> ABC + D reactions. The approach is an extension to 4-atom reactions of a version of the reactant-product decoupling (RPD) approach, applied previously to 3-atom reactions ( J. Chem. Phys. 2001, 114 , 1601 ). The approach partitions the coordinate space of the reaction into separate reagent, strong-interaction, and product regions, using a system of artificial absorbing and reflecting potentials. It employs a partitioned version of the split-operator propagator, which is more efficient than partitioning the (exact) time-dependent Schrodinger equation. The wave packet bounces off a reflecting potential in the entrance channel, which generates a source term; this is transformed efficiently from reagent to product Jacobi coordinates by exploiting some simple angular momentum properties. The efficiency and accuracy of the method is demonstrated by numerical tests on the benchmark OH + H(2) --> H(2)O + H reaction.
我们描述了一种用于计算4原子AB + CD → ABC + D反应的态-态量子动力学的量子波包方法。该方法是反应物-产物解耦（RPD）方法的一个版本对4原子反应的扩展，此前该方法已应用于3原子反应（《化学物理杂志》，2001年，第114卷，第1601页）。该方法使用人工吸收和反射势系统将反应的坐标空间划分为单独的反应物、强相互作用和产物区域。它采用了分裂算符传播子的分区版本，这比分时依赖薛定谔方程进行分区更有效。波包在入射通道中从反射势反弹，产生一个源项；通过利用一些简单的角动量性质，该源项可以有效地从反应物雅可比坐标转换为产物雅可比坐标。通过对基准反应OH + H(2) → H(2)O + H的数值测试，证明了该方法的效率和准确性。
