Institut für Chemie und Biochemie, Freie Universität Berlin, 14195 Berlin, Germany.
J Chem Phys. 2013 Sep 14;139(10):104315. doi: 10.1063/1.4820881.
We propose a method to steer the outcome of reactive atom-diatom scattering, using rotational wavepackets excited by strong non-resonant laser pulses. Full close-coupled quantum mechanical scattering calculations of the D+H2 and F+H2 reactions are presented, where the H2 molecule exists as a coherent superposition of rotational states. The nuclear spin selective control over the molecular bond axis alignment afforded by the creation of rotational wavepackets is applied to reactive scattering systems, enabling a nuclear spin selective influence to be exerted over the reactive dynamics. The extension of the conventional eigenstate-to-eigenstate scattering problem to the case in which the initial state is composed of a coherent superposition of rotational states is detailed, and a selection of example calculations are discussed, along with their mechanistic implications. The feasibility of the corresponding experiments is considered, and a suitable simple two pulse laser scheme is shown to strongly differentiate the reactivities of o-H2 and p-H2.
我们提出了一种使用强非共振激光脉冲激发的旋转波包来控制反应原子-双原子散射结果的方法。本文给出了 D+H2 和 F+H2 反应的全紧密耦合量子力学散射计算，其中 H2 分子以旋转态的相干叠加形式存在。通过创建旋转波包，可以对分子键轴取向进行核自旋选择性控制，从而对反应动力学施加核自旋选择性影响。详细描述了将传统的本征态到本征态散射问题扩展到初始态由旋转态相干叠加组成的情况，并讨论了一些示例计算及其机理意义。考虑了相应实验的可行性，并展示了一种合适的简单双脉冲激光方案，该方案可强烈区分 o-H2 和 p-H2 的反应性。
