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\begin{document}

\title{Carbonyl Oxide Chemistry in Water Cluster: An Extended Computational
Study}



\author[1]{Chayanika Kashyap}%
\author[1]{Indrani Baruah}%
\author[1]{Shahnaz Rohman}%
\author[1]{Sabnam Ullah}%
\author[1]{Amlan Kalita}%
\author[1]{Gargi Borgohain}%
\author[1]{Ankur Guha}%
\affil[1]{Cotton University}%


\vspace{-1em}



  
  \date{May 24, 2024}


\begingroup
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\selectlanguage{english}
\begin{abstract}
An extended computational approach has been utilized to explore the
reactions of acids with carbonyl oxide, also known as Criegee
intermediate (CI). The reactions were explored inside water cluster
containing 50 water molecules. All possibilities of product formation
were considered. Among the considered acids, the rate of 1,4-insertion
follows the order - HCOO \textless{} HCl \textless{} HNO3. The most
stable products of the reactions between the considered acids and CI
have been identified.%
\end{abstract}%



\sloppy


\textbf{}

\par\null

\textbf{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.\textsuperscript{1-4} It is found that tropospheric
alkenes are the most significant source of Criegee
intermediates.\textsuperscript{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.\textsuperscript{8-10}Studies found that some acids like
HCl, H\textsubscript{2}SO\textsubscript{4}, HNO\textsubscript{3}, HCOOH
etc. are embedded on the surface of stratospheric region condensing with
H\textsubscript{2}O, they are also known as polar stratospheric
particles, play a major role in scavenging CIs. During these scavenging
reaction with acids, atmospheric H\textsubscript{2}O budget are
remarkably influenced.\textsuperscript{11}

Early experimental data showed fast reactions of CI with formic acids
(rate constant,
k\textsubscript{HCOOH}=1*10\textsuperscript{-11}cm\textsuperscript{3}molecule-\textsuperscript{1}s\textsuperscript{-1}),
hydrochloric acids (rate constant, k\textsubscript{HCl}=
4.0*10\textsuperscript{-11}cm\textsuperscript{3}molecule\textsuperscript{-1}s\textsuperscript{-1})
and nitric acids (k\textsubscript{HNO3} = 5.4
*10\textsuperscript{-10}cm\textsuperscript{3}molecule\textsuperscript{-1}s\textsuperscript{-1}),
forming good yields.\textsuperscript{12-16} Their reaction rates are
suggested with the help of their reaction rate co-efficient
values.\textsuperscript{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.\textsuperscript{19,20} The obtained experimental data were
also in agreement with theoretical values.\textsuperscript{11} Vereecken
performed quantum chemical calculation to find out the probable barrier
less pathways of these CI-acid reactions in gaseous
phase.\textsuperscript{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.

\textbf{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 \emph{abinitio} calculations. The gradient and hessian
calculations were performed using M06-2X/6-311+G* level of
theory.\textsuperscript{21} We have used two layer
ONIOM\textsuperscript{22} 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, \textless{} 0.5\%. All these calculations were
performed using Gaussian 16 suite of program.\textsuperscript{23}

\textbf{3. Result and discussion}

\textbf{3.1 Water Cluster}

Fig 1 shows the TIP4P minimum energy structure of water cluster
containing 50 water molecules. This cluster has been used to simulate
all the reaction pathways discussed below.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image2/image2}

\end{center}
\end{figure}

\textbf{Fig 1} . TIP4P energy minimized structure of water cluster
containing 50 water molecules.

\textbf{3.2 Formation of Criegee Intermediate (CI):} Carbonyl oxides or
CIs are those atmospheric intermediate which significantly act as
non-photolytic source of many tropospheric reaction processes.
Johnson\emph{et.al} proved that the carbonyl oxides are produced via
alkene ozonolysis having significant amount of internal energy to
undergo either unimolecular or bimolecular reactions depending upon
their stability.\textsuperscript{20} As tropospheric abundances of
alkenes and ozone are relatively higher, it is worthwhile to study the
formation of CI through the reaction between
C\textsubscript{2}H\textsubscript{4}with O\textsubscript{3}. Fig 2 shows
the reaction energetic.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image3/image3}

\end{center}
\end{figure}

\textbf{Fig 2} . Energetic for the formation of CI by the reaction of
C\textsubscript{2}H\textsubscript{4} with O\textsubscript{3}. The
optimized geometries of the intermediates and transition states were
also shown. Bond lengths are in \selectlanguage{ngerman}Å.

CI-formation takes place via ozonolysis of
C\textsubscript{2}H\textsubscript{4}. First step is 1,3-dipolar
cycloaddition of ozone to the double bond of ethane leading to primary
ozonide or 1\textsuperscript{st} molozonide, \textbf{1} . The reaction
is found to be exergonic by 75.3 kcal/mol. In 2\textsuperscript{nd}
step, the carbonyls (as 1,3-compounds) again undergo 1,3-cycloaddition,
leading to the formation of secondary ozonide \textbf{2} (more stable
than primary ozonide). The 3\textsuperscript{rd} step is the breaking of
C-O bonds to generate the Criegee intermediate (carbonyl oxides) and
H\textsubscript{2}CO which involves a barrier of 25.1 kcal/mol. Overall,
the formation of CI is exergonic suggesting the high rate of the
reaction between C\textsubscript{2}H\textsubscript{4} and
O\textsubscript{3}.

We then turned our attention to investigate all the possible reaction
channels of some acids with CI. The choice of the acids namely,
hydrochloric acid, formic acid and nitric acid for the reaction with CI
is stimulated by their high abundance in atmosphere.

\textbf{3.3} \textbf{Reactions between hydrochloric acids and CI} : For
the co-reactant HCl, two reaction channels are considered one involving
the attack of H atom of HCl to the O atom of CI while the other one
involves concomitant attack of H of HCl to the terminal O of CI and Cl
of HCl to the C atom of CI resulting in the formation of a cyclic
transition state \textbf{TS-2} (Fig 3). The energy profile diagram is
shown in Fig 3.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image4/image4}

\end{center}
\end{figure}

\textbf{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 \textbf{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 \textbf{TS2} with a barrier of 17.75
kcal/mol. This \textbf{TS2} gives a relevant
\textbf{INT}ClCH\textsubscript{2}OOH (chlorinated methylhydroxyperoxide)
or thermally fragmented into chlorinated methoxy and hydroxyl radicals
(\textbf{PROD-1} ). \textbf{INT} may lead to the most stable products
chlorinated methanal and water (\textbf{PROD-3} ) via a
cyclic\textbf{TS3} . The energy barrier for this process is 19.1
kcal/mol. The formation of \textbf{PROD-3} is highly exergonic and is
the most stable product.

\textbf{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.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image5/image5}

\end{center}
\end{figure}

\textbf{Fig 4} . Energetic of the reaction between CI and HCOOH in water
cluster.

Among these pathways, three reactions are initiated through a
cyclic\textbf{TS1} with a barrier of 46.44 kcal/mol which is formed due
to 1,4-insertion of CI to HCOOH. The \textbf{TS1} then leads to one
common intermediate hydroperoxymethylformate \textbf{INT} (HPMF). The
formation of this INT is endergonic by 44.01 kcal/mol. This \textbf{INT}
is bifurcated to \textbf{TS2} and \textbf{TS3} at the energy level of
90.06 kcal/mol and 44.96 kcal/mol respectively. The \textbf{TS2} yields
highly stabilized product (\textbf{PROD-2} ) while \textbf{TS3} gives a
mixture of radical product (\textbf{PROD-3} ). Another mixture of
product (\textbf{PROD-4} ) is found from \textbf{TS3} via another
\textbf{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 via \textbf{TS4} with a low
barrier of 10.17 kcal/mol.

\textbf{3.5 Reactions between nitric acids and CI:} For Nitric acid, as
the co-reactant for CI, three product formation pathways are shown in
Fig 5.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image6/image6}

\end{center}
\end{figure}

\textbf{Fig 5} . Energetic of the reaction between CI and
HNO\textsubscript{3} in water cluster.

The different sets of products can be formed for the reaction between CI
and HNO\textsubscript{3}. The formation of \textbf{PROD-1} is exergonic
while the formation of \textbf{PROD-2} is endergonic. The attainment of
these two products is sourced from same intermediate \textbf{INT} which
is at the -47.0 kcal/mol in the energy profile diagram. This\textbf{INT}
is attained via a transition state (\textbf{TS1} ) with a barrier of
11.42 kcal/mol. The INT then forms two products (\textbf{PROD-1} and
\textbf{PROD-2} ) via two transition states (\textbf{TS2} and
\textbf{TS3} ). \textbf{TS3} lies very high in energy and thus the
formation of \textbf{PROD-2} is less likely. Third
product\textbf{PROD-3} is obtained by proton abstraction of CI from
nitric acid via a transition state \textbf{TS4} . The energy barrier for
the formation of \textbf{PROD-3} is only 6.96 kcal/mol and the formation
of\textbf{PROD-3} is slightly endergonic (1.99 kcal/mol). From the
energy barrier values, it is evident that proton abstraction from nitric
acid will be easiest having highest rate constant values which is in
agreement with previous theoretical calculations in gaseous
phase.\textsuperscript{11}

\textbf{4. Conclusions}

All the reaction channels of Criegee intermediate (CI) with different
acids held within a water cluster having 50 water molecules have been
studied using high level ONIOM method (CCSD:M06-2X). Several products
have been identified with low barrier for their formation. As the
atmosphere contains a large quantity of water, the reactions studied
herein have a good implication towards understanding the degradation
mechanism of the acids considered herein. The barrier for 1,4-insertion
pathway depends on the acid. The trend of barrier for the 1,4-insertion
pathway follows the order: HCOO \textless{} HCl \textless{}
HNO\textsubscript{3}. This is also in tune with previous experimental
values of rate constants.\textsuperscript{12-16} This study provides all
the possible pathways of degradation of these acids on reacting with CI.

\textbf{Acknowledgement}

A. K. G. thanks the Science and Engineering Research Board (SERB),
Government of India for providing financial assistance in the form of a
project (project no. ECR/2016/001466). G. B. thanks DST for financial
support (DST/INSPIRE/04/2017/003051).

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