Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom.
J Chem Phys. 2011 Jan 14;134(2):024309. doi: 10.1063/1.3525541.
We extend to full dimensionality a recently developed wave packet method [M. T. Cvitaš and S. C. Althorpe, J. Phys. Chem. A 113, 4557 (2009)] for computing the state-to-state quantum dynamics of AB + CD → ABC + D reactions and also increase the computational efficiency of the method. This is done by introducing a new set of product coordinates, by applying the Crank-Nicholson approximation to the angular kinetic energy part of the split-operator propagator and by using a symmetry-adapted basis-to-grid transformation to evaluate integrals over the potential energy surface. The newly extended method is tested on the benchmark OH + H(2) → H(2)O + H reaction, where it allows us to obtain accurately converged state-to-state reaction probabilities (on the Wu-Schatz-Fang-Lendvay-Harding potential energy surface) with modest computational effort. These methodological advances will make possible efficient calculations of state-to-state differential cross sections on this system in the near future.
我们将最近开发的一种波包方法[M. T. Cvitaš 和 S. C. Althorpe, J. Phys. Chem. A 113, 4557 (2009)]扩展到全维，用于计算 AB + CD → ABC + D 反应的态态量子动力学，同时也提高了该方法的计算效率。这是通过引入一组新的产物坐标，通过对分裂算符传播子的角动能部分应用 Crank-Nicholson 逼近，以及通过使用对称自适应基到网格变换来评估势能面上的积分来实现的。新扩展的方法在基准 OH + H(2) → H(2)O + H 反应上进行了测试，它允许我们以适度的计算工作量准确地获得收敛的态态反应概率（在 Wu-Schatz-Fang-Lendvay-Harding 势能面上）。这些方法上的进步将使得在不久的将来能够有效地计算该体系的态态微分截面。
