Reactant-Product Decoupling Technique Using the Intermediate Coordinate Method.

Although the reactant-product decoupling (RPD) technique was proposed over two decades ago, it remains an efficient approach for calculating product state-resolved information on some simple direct reactions using the quantum wave packet method. In the past, usually the RPD technique employed the collocation method to transform the wave function between reactant and product arrangements, which requires quite large computational efforts. In this work, the intermediate coordinate (IC) method is employed to realize the RPD technique. Numerical examples demonstrate that this new IC RPD (IRPD) technique has superior computational efficiency compared with the original method employing the collocation method. Especially, the new IRPD technique significantly saves disk space and computer memory. To illustrate the features of our new method, the total reaction probabilities of the H + H 2 , H + Br 2 , and F + H 2 reactions with J = 0 and the differential cross sections of the H + H 2 and F + H 2 reactions at a series of collision energy are calculated and presented. With this efficient and effective new RPD technique, the Li + HF reaction, which involves sharp resonances with long-range wave functions in the van der Waals wells in both the reactant and product arrangements, is also calculated with several J at the product state-resolved level to reveal the ability of the RPD technique for describing resonance wave functions. With these numerical examples, it is found that, for the reaction with resonances, the RPD approach should be applied carefully. Otherwise, it is very possible that the resonances could disappear with the application of the RPD technique.