Reaching the cold regime: S(^1D) + H_2 and the Role of Long-Range Interactions in Open Shell Reactive Collisions

TL;DR

This study calculates reactive cross-sections for S(^1D) with H_2 at low temperatures, emphasizing the importance of long-range interactions and quantum effects, and compares results with recent experimental data.

Contribution

It introduces an accurate quantum scattering model incorporating long-range interactions for open shell reactions at low temperatures, aligning well with experimental measurements.

Findings

Good agreement with experimental rate constants

Observation of oscillating cross-section features for para-hydrogen

Long-range electrostatic and dispersion interactions significantly influence reactivity

Abstract

Reactive cross-sections for the collision of open shell S(^1D) atoms with ortho- and para-hydrogen, in the kinetic energy range 1-120 K, have been calculated using the hyperspherical quantum reactive scattering method developed by Launay et al. [Chem. Phys. Lett. 169, 473 (1990)]. Short-range interactions, described using the {\em ab initio} potential energy surface by Ho et al. were complemented with an accurate description of the long-range interactions, where the main electrostatic (~R^{-5}) and dispersion (~ R^{-6}) contributions were considered. This allows the comparison with recent experimental measurements of rate constants and excitation functions for the title reaction at low temperatures [Berteloite et al., Phys. Rev. Lett., 2010]. The agreement is fairly good. The behavior in the considered energy range can be understood on the average in terms of a classical Langevin (capture) model, where the centrifugal barriers determine the amount of reactive flux which reaches the barrierless transition state. Additionally, the structure of the van der Waals well provides temporal trapping at short distances thus allowing the system to find its way to the reaction at some classically-forbidden energies. Interestingly, the cross-section for para-hydrogen shows clearly oscillating features associated to the opening of new partial waves and to shape resonances which may be amenable to experimental detection.