On the Reactivity of Ti⁺(⁴F,²F). Reaction of Ti⁺ with OH₂

Abstract

The reaction of Ti+(4F,2F) + OH2 has been studied in detail for both doublet and quartet spin states. The only exothermic products are TiO+(2Δ) and H2; formation of several endothermic products is also examined. An in-depth analysis of the reaction paths leading to each of the observed products is given, including various singlet, triplet, and quartet minima, several important transition states, and a discussion of the two H2 elimination mechanisms proposed in the literature. The experimentally observed spin-forbidden crossing is given a possible explanation. Throughout this work comparison to experimental results in energetics, reaction products, and suggested mechanisms has been central.