State-to-state chemiluminescence in reactions of Mn atoms with S2Cl2

Abstract

A combined experimental and time-dependent density functional theory (TDDFT) investigation of the title reaction is presented. Both ‘hot’ and ‘cold’ laser-ablated Mn atom beams have been employed to determine the translational excitation functions for production of MnCl*(c⁵Σ⁺, d⁵Π, e⁵Δ, e⁵Σ⁺, A⁷Π). Analysis in terms of the multiple line-of-centres approach shows that the ‘hot’ results are dominated by reactions of the second metastable state of Mn, z⁸P_J, all with very low thresholds; while the first metastable state, a⁶D_J, and the ground state, a⁶S, are the precursors in the ‘cold’ results, all with significant excess barriers. The post-threshold behaviour of most z⁸P_J and a⁶D_J reaction channels implies that the transition states shift forward with increasing collision energy. The TDDFT calculations suggest that, while Mn*(z⁸P_J, a⁶D_J) insertion into the S–Cl bond is facile, the observed chemiluminescence channels mostly derive from abstraction in a preferred linear Mn–Cl–S configuration, and that the low z⁸P_J thresholds originate from attractive but excited reagent potentials which either reach a seam of interactions in the product valley or (in the c⁵Σ⁺ case) lead to an octet potential very close in energy to the product sextet. The excess barriers in the Mn*(a⁶D_J) and Mn(a⁶S) reactions appear for the most part to derive from exit channel mixing with lower-lying product potentials. The observed transition state shifts are consistent with the system being forced to ride up the repulsive wall of the entrance valley as collision energy increases, the location of that wall being different for the z⁸P_J and a⁶D_J cases.