Dissociation of hydrogen peroxide in water and methanol through a biased molecular dynamics investigation.

The two dissociation channels of HOOH, namely, HOOH and HOOH, in water and methanol are investigated using umbrella-sampling ab initio molecular dynamics. Our potential of mean force calculations reveals the HOOH dissociation to be more favorable in methanol with a free energy barrier of 7.56 kcal/mol, while the HOOH dissociation possesses a free energy barrier of 11.46 kcal/mol. In water, the HOOH dissociation channel is more favorable (8.25 kcal/mol), while the HOOH dissociation process requires a higher free energy (11.28 kcal/mol). Such reaction favorability can be explained by inspecting the formation of secondary radical species during the course of multiple hydrogen donating-accepting processes in each reaction channel. The radical species, that is, H3 O• (observed in water) and CH3 OH2• (observed in methanol), are the first subordinate species upon the HOOH dissociation. For the HOOH dissociation channel in methanol, the secondary species such as water and formaldehyde can be observed, while the re-generation of HOOH in water can be spotted.