1. Introduction: In atmosphere, ozone molecule occurs as open
shell singlet di-radical. Ozone easily attack the double bond containing
compounds and oxidized them by attacking at double bonded positions,
which generates a highly reactive Criegee intermediate (CI), also known
as carbonyl oxide.1-4 It is found that tropospheric
alkenes are the most significant source of Criegee
intermediates.5-7 Tropospheric alkenes are strongly
localized and short chain alkenes are more usual to undergo ozonolysis.
The general mechanism of alkene ozonolysis is shown below –
These produced CIs are found to have excess internal energy to undergo
unimolecular processes, generally. But with acidic particles, these CIs
undergo bimolecular reaction so efficiently.8-10Studies found that some acids like HCl,
H2SO4, HNO3, HCOOH etc.
are embedded on the surface of stratospheric region condensing with
H2O, they are also known as polar stratospheric
particles, play a major role in scavenging CIs. During these scavenging
reaction with acids, atmospheric H2O budget are
remarkably influenced.11
Early experimental data showed fast reactions of CI with formic acids
(rate constant,
kHCOOH=1*10-11cm3molecule-1s-1),
hydrochloric acids (rate constant, kHCl=
4.0*10-11cm3molecule‑1s-1)
and nitric acids (kHNO3 = 5.4
*10-10cm3molecule-1s-1),
forming good yields.12-16 Their reaction rates are
suggested with the help of their reaction rate co-efficient
values.16-18 The obtained high rate co-efficient
values suggested that acids play a key role in scavenging CI in the
atmosphere leading to the formation of low-volatile but highly oxidized
molecules.19,20 The obtained experimental data were
also in agreement with theoretical values.11 Vereecken
performed quantum chemical calculation to find out the probable barrier
less pathways of these CI-acid reactions in gaseous
phase.11 As it has been already discovered that water
budget plays a significant role in atmosphere, so here in our study, all
the possible pathways of the CI-acid reactions are studied in water
cluster containing 50 water molecules using high level computational
chemistry approach.
2. Computational details: The water cluster containing 50
molecules of water was energy minimized using TIP4P model for water by
using leap module of AMBER18 package. Steepest descent method was used
for energy minimization and conjugate gradient method to discard any
unfavourable interactions. The energy minimized water cluster was used
for all other abinitio calculations. The gradient and hessian
calculations were performed using M06-2X/6-311+G* level of
theory.21 We have used two layer
ONIOM22 calculations by using CCSD/6-311++G** for the
reactants and M06-2X/6-311+G* for the surrounding water molecules.
Intermediates were characterized by all real values of the hessian
matrix while transition states were characterized by one imaginary value
of the hessian matrix. Open shell species were treated with unrestricted
formalism. Unless otherwise noted, spin contamination values were
negligibly small, < 0.5%. All these calculations were
performed using Gaussian 16 suite of program.23