Does ozone have a barrier to dissociation and recombination?

Global permutationally invariant potential energy surface for ozone forming reaction

“…This behavior of the PES is consistent with earlier calculations by other authors. 13,17,18 Note, however, that those earlier calculations were carried out ρ (Bohr) along the minimum energy path only, while here we have a global 3D-PES. On our PES the vdW well is ∼ 216 cm…”

“…11, where he lowered the barrier into a reef, matching the results of higher-level calculations along the MEP. 13 This was done in a semi-empirical fashion, by adding the analytic correction function 11 to the PES of Schinke. 9 In the new global surface constructed here such correction is not needed anymore.…”

“…Second, that surface contained an artifact -a barrier along the minimum energy path (MEP) to dissociation. 13 The height of the barrier was only 47 cm −1…”

“…15,16 There were several attempts to determine the level of theory required to compute a better surface for O 3 . Higher level electronic structure calculations by several authors carried out along the minimum energy path 13,17,18 showed that top of the barrier is, indeed, below the dissociation limit, which transforms barrier into a "submerged reef." It was also suggested that the improvement to dissociation energy can be achieved by increasing the basis set size.…”

Communication: Highly accurate ozone formation potential and implications for kinetics

“…Since its initial discovery, this "reef" feature has been found in all high-level ab initio calculations up to the complete basis set (CBS) limit. 17,18,21,22 As a result, it has been taken as a true signature of the O 3 PES and was incorporated into the widely used hybrid O 3 PES developed by Babikov et al, 19 as shown in Fig. 1.…”