The dawn of hydrogen and halogen bonds and their crucial role in collisional processes probing long-range intermolecular interactions

Abstract

This perspective review focuses on the results of an internally consistent study developed in the Perugia laboratory, centered on the fundamental interaction components that, at large intermolecular distances, determine the formation of weak intermolecular hydrogen (HB) and halogen (XB) bonds. This investigation exploits old and novel molecular beam scattering experiments involving several gaseous prototypical systems. In particular, we focus on the kinetic energy dependence of the total (elastic + inelastic) integral cross-sections. Of particular interest is the measure of quantum interference patterns in the energy dependence of cross-sections of targeted systems and their shift compared to that of known reference systems. We interpreted these findings as interaction energy stabilization components, such as charge transfer, σ-hole, and polar flattening, that emerge at intermediate separation distance ranges and selectively manifest for specific geometries of collision complexes. Another significant observable we discuss is the absolute value of the cross-section and its dependence on permanent multipole moments of the collisional partners. Specifically, we show how the spontaneous orientation of rotationally cold and polar molecules, due to the electric field gradient associated with the interaction between permanent multipole moments, can significantly modify the magnitude of the total cross-section, even at high values of the impact parameter. We are confident that the present results can help extend the force field formulation to various interacting systems and carry out molecular dynamics simulations under conditions of application interest.