Fig 5 . Energetic of the reaction between CI and HCOOH in water cluster.
Among these pathways, three reactions are initiated through a cyclicTS1 with a barrier of 46.44 kcal/mol which is formed due to 1,4-insertion of CI to HCOOH. The TS1 then leads to one common intermediate hydroperoxymethylformate INT (HPMF). The formation of this INT is endergonic by 44.01 kcal/mol. This INT is bifurcated to TS2 and TS3 at the energy level of 90.06 kcal/mol and 44.96 kcal/mol respectively. The TS2 yields highly stabilized product (P2 ) while TS3 gives a mixture of radical product (P3 ). Another mixture of product (P4 ) is found from TS3 via another TS5 . The energy barrier associated with this path is very high. Another reaction route involves proton abstraction from formic acid by CI to generate an acid radical (P1 ) via TS4 with a low barrier of 10.17 kcal/mol.
The calculate rate constant for the product P1 formation is 2.5 X 10-11 cm3molecule‑1 s-1 while that for product P2 formation is 3.1 X 10-13cm3 molecule‑1s-1. The calculate overall rate constant value kTotal is 2.5 X 10-11cm3 molecule‑1 s-1which is at least two times higher than the gas phase reaction (kTotal = 1.1 X 10-11cm3 molecule‑1s-1).14 The calculated B. R. suggests that the most dominating reaction channel is the formation of the acid radical (P1 , 98%).
3.5 Reaction between nitric acid and CI: For Nitric acid, as the co-reactant for CI, three product formation pathways are shown in Fig 6.