Abstract

Modifications in atomic alignment and in molecular alignment/orientation determine a different structure of the adduct, formed by collisions of reagents, which represents the precursor state of many elementary chemical–physical processes. The following evolution of the system is directly controlled by the confinement of interacting partners in such a precursor state. However, a deep characterization of these phenomena is still today not fully available, especially when weak intermolecular forces are operative, although the inquiry is of general relevance for the control of the stereodynamics of processes, occurring under a variety of conditions both in gas phase and at surface. In this paper recent advances in the knowledge of the selective role of atomic alignment and molecular orientation effects on the stereodynamics of chemi-ionization reactions will be presented and discussed. These advances represent a basic step along a path whose final target is the complete and internally consistent rationalization and revaluation of the experimental findings already obtained, and published, in our and in other laboratories on chemi-ionization reactions involving as reagent molecules which are of great relevance in several fields. The basic idea is to export important guidelines provided by a recent detailed study of chemi-ionization of noble gas atoms to more complex reactions involving molecules. The main focus of the present paper is on the quantum confinement effects of valence electrons within the reaction transition state.

Graphic abstract

中文翻译：

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化学电离反应的前体状态和各向异性分子间力对价电子的限制

摘要

原子排列和分子排列/取向的改变决定了加成物的不同结构，它是由试剂的碰撞形成的，它代表了许多基本化学-物理过程的前体状态。系统的后续发展直接受到处于这种前体状态的相互作用伙伴的限制。然而，尽管对于气态和气态的各种条件下发生的过程的立体动力学的控制具有普遍意义，但今天仍无法完全获得对这些现象的深入表征，尤其是在弱分子间作用力起作用的情况下。在表面。在本文中，将介绍和讨论原子排列和分子取向效应对化学电离反应的立体动力学的选择性作用的认识的最新进展。这些进展代表了迈出的基本一步，其最终目标是在我们和其他实验室中完成并在内部实验室对已获得和发表的有关化学电离反应的实验结果进行彻底和合理化的重新评估，其中涉及作为重要分子的化学分子。在几个领域的相关性。基本思想是将最近进行的稀有气体原子化学电离的详细研究提供的重要指南导出到涉及分子的更复杂反应中。本文的主要重点是价电子在反应过渡态内的量子约束效应。

图形摘要