Fig 3 . Energetic of the reaction between CI and HCl in water
cluster.
The first reaction route is normal proton abstraction by CI from HCl
which proceed via TS1 with a barrier of 13.56 kcal/mol and
generates a chloride radical, which can further initiate chain
reactions. The second reaction channel involves 1,3-insertion of HCl to
CI which forms a 5-memebered TS2 with a barrier of 17.75
kcal/mol. This TS2 gives a relevant INTClCH2OOH (chlorinated methylhydroxyperoxide) or
thermally fragmented into chlorinated methoxy and hydroxyl radicals
(PROD-1 ). INT may lead to the most stable products
chlorinated methanal and water (PROD-3 ) via a cyclicTS3 . The energy barrier for this process is 19.1 kcal/mol. The
formation of PROD-3 is highly exergonic and is the most stable
product.
3.4 Reactions between formic acids and CI: Four reaction
pathways have been shown for the reaction between CI and formic in this
study as shown in Fig 4.