Stereodynamical Effects by Anisotropic Intermolecular Forces.

ABSTRACT

Electric and magnetic field gradients, arising from sufficiently strong anisotropic intermolecular forces, tend to induce molecular polarization which can often modify substantially the results of molecular collisions, especially at low rotational temperatures and low collision energies. The knowledge of these phenomena, today still not fully understood, is of general relevance for the control of the stereo-dynamics of elementary chemical-physical processes, involving neutral and ionic species under a variety of conditions. This paper reports on results obtained by combining information from scattering, spectroscopic and reactivity experiments, within a collaboration between the research groups in Perugia and Trento. We addressed particular attention to the reactions of small atomic ions with polar neutrals for their relevance in several environments, including interstellar medium, planetary atmospheres, and laboratory plasmas. In the case of ion-molecule reactions, alignment/orientation is a general phenomenon due to the electric field generated by the charged particle. Such phenomenon originates critical stereo-dynamic effects that can either suppress (when the orientation drives the collision complex into non-reactive or less reactive configurations), or enhance the reactivity (when orientation confines reagents in the most appropriate configuration for reaction). The associated rate coefficients show the propensity to follow an Arrhenius and a non-Arrhenius behavior, respectively.