Angewandte

Communications Chemie

International Edition: DOI: 10.1002/anie.201702722

Atmospheric Chemistry German Edition: DOI: 10.1002/ange.201702722

Surprising Stability of Larger Criegee Intermediates on

Aqueous Interfaces
Jie Zhong+, Manoj Kumar+, Chong Q. Zhu, Joseph S. Francisco,* and
Xiao C. Zeng*

Angewandte
Chemie
7740 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2017, 56, 7740 –7744

Communications
Abstract: Criegee intermediates have implications as key
intermediates in atmospheric, organic, and enzymatic reac-
tions. However, their chemistry in aqueous environments is
relatively unexplored. Herein, Born–Oppenheimer molecular
dynamics (BOMD) simulations examine the dynamic behav-
ior of syn- and anti-CH3CHOO at the air–water interface. They
show that unlike the simplest Criegee intermediate (CH2OO),
both syn- and anti-CH3CHOO remain inert towards reaction
with water. The unexpected high stability of C2 Criegee
intermediates is due to the presence of a hydrophobic methyl
substituent on the Criegee carbon that lowers the proton
transfer ability and inhibits the formation of a pre-reaction
complex for the Criegee–water reaction. The simulation of the
larger Criegee intermediates, (CH3)2COO, syn- and anti-
CH2C(CH3)C(H)OO on the water droplet surface suggests
that strongly hydrophobic substituents determine the reactivity
of Criegee intermediates at the air–water interface.
Even since the direct detection of Criegee intermediates in
the gas-phase,[1] understanding their structures, spectroscopy,
reactivity, and their implications to atmospheric chemistry[2]
has become a hot topic of research. Criegee intermediates are
carbonyl oxides that are formed in the ozone–olefin cyclo-
addtions.[3] Owing to their high reactivity, the Criegee
intermediates are believed to play a crucial role in the
tropospheric budgets of hydroxyl radicals,[4] acids,[5] sulfates,
and secondary organic aerosols.[6] Among all the bimolecular
Criegee reactions, the Criegee–water reaction is viewed as the
most important one in the troposphere. This is because the
concentration of water in the troposphere is orders of
magnitude higher than other atmospheric trace gases, such
as SO2, NO2, organic or inorganic acids. As a result, reactions
of Criegee intermediates with water could strongly affect the
atmosphere models of Criegee chemistry.
The reactivity of Criegee intermediates towards gas-phase
water has been widely investigated,[7] which was found
significantly affected by the nature and location of the
substituents. Criegee intermediates having a methyl substitu-
ent in the anti position react faster than Criegee intermediates
having a methyl substituent in syn position.[8] Figure 1 shows
the reaction profiles for the reactions of C1 and C2 Criegee
intermediates with water monomer at the CCSD(T)/aug-cc-
pVTZ//M06-2X/aug-cc-pVTZ level of theory. The barrier for
the CH2OO–H2O reaction, with respect to the pre-reaction
complex, is 9.2 kcal mol@1. This barrier is 3.8 kcal mol@1 lower
[*] J. Zhong,[+] Dr. M. Kumar,[+] C. Q. Zhu, Prof. J. S. Francisco,
Prof. X. C. Zeng
Department of Chemistry
University of Nebraska-Lincoln
Lincoln, NE 68588 (USA)
E-mail: jfrancisco3@unl.edu
xzeng1@unl.edu
Prof. X. C. Zeng
Beijing Advanced Innovation Center for Soft Matter Science and
Engineering, Beijing University of Chemical Technology
Beijing, 100029 (China)
[+] These authors contributed equally to this work.
Supporting information for this article can be found under:
https://doi.org/10.1002/anie.201702722.
Angew. Chem. Int. Ed. 2017, 56, 7740 –7744 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Chemie
Figure 1. CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ calculated reac-
tion profiles for the reactions of C1 and C2 Criegee intermediates with
water. The zero-point-corrected electronic energies are given in kcal
mol@1.
than that for the syn-CH3CHOO-H2O reaction, whereas
1.3 kcal mol@1 higher than that for the anti-CH3CHOO–H2O
reaction. The results indicate that the anti-CH3CHOO has
greater reactivity towards water monomer in the gas phase,
followed by CH2OO and syn-CH3CHOO. Recently, the
reaction of larger Criegee intermediate, (CH3)2COO with
water was found to be slower than that with SO2,[9] suggesting
that the reactivity of a Criegee intermediate toward the gas-
phase water strongly depends on its conformation.
In the troposphere, the water molecules have high chance
to nucleate and form aerosols, fog, or clouds, which are
believed to play a key role in atmospheric chemistry.[10] The
abundance of aerosols can rise up to approximately 108–
109 m@3, and the maximum surface area of the aerosols in
clouds amounts to about 10@9 m2.[11] Recently, the Quantum
Mechanics/Molecular Mechanics (QM/MM) simulations
show that the simplest Criegee intermediates (CH2OO)
react with water-droplet surface on the order of a few
picoseconds, 2–3 orders of magnitude shorter than that in the
gas phase.[12] This suggests that the air–water interface, which
is the characteristic of the surface of oceans, lakes, and
atmospheric aerosols, can play a more direct role in the
Criegee/water reactions due to their ability to react, concen-
trate and align reacting species in a water restricting environ-
ment. However, the conformer-dependent reactivity of the
Criegee intermediates at the air–water interface is yet to be
examined. It is commonly believed that the gas-phase anti-
CH3CHOO reacts faster with trace gases than the syn-
CH3CHOO. However, our Born–Oppenheimer molecular
dynamics (BOMD) simulations, that we report here, show
that unlike the simplest Criegee intermediate, CH2OO, both
syn- and anti-CH3CHOO at the air–water interface exhibit
inertness towards the water reaction. The hydrophobicity of
a methyl substituent appears to play a crucial rule in
stabilizing Criegee intermediates on the aqueous surface.
All BOMD simulations were performed using the density
functional theory (DFT) method implemented in the CP2K
code.[13] The simulation details are shown in the Supporting
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Communications Chemie

Information. Figure 2 shows the time-dependent

profiles of the two key distances involving the
terminal oxygen (O2) and carbon (C1) of the Criegee
moiety and interfacial water molecules, that is,
O2···Hw and C1···Ow. For CH2OO at air–water inter-
face (Figure 2 B), the O2···Hw bond shrinks to 1.0 c at
4.5 ps, and simultaneously, the C···Ow bond shrinks to
1.4 c (Movie S1). This represents a typical reaction
of CH2OO with interfacial water. In contrast, for syn-
and anti-CH3CHOO at the air–water interface (Fig-
ure 2 C,D), both O2···Hw and C···Ow bonds remain
unchanged over the simulation time of 35 ps for syn-
CH3CHOO and anti-CH3CHOO, respectively, dem-
onstrating surprisingly high stability of C2 Criegee
intermediates on the aqueous surface (Movies S2–
S5). Note that the simulations from different initial
configurations, which accounted for a total simulation
time of 70 ps for syn-CH3CHOO and 65 ps for anti-
CH3CHOO, give the same results, as shown in
Figure S1.
Figure 2. A) An illustration of the interaction of anti-CH3CHOO with surround-
We next examined the factors responsible for the ing interfacial water molecules. The O2···Hw and C1···Ow distances versus
high stability of CH3CHOO at the air–water inter- simulation time for B) CH2OO, C) syn-CH3CHOO, and D) anti-CH3CHOO at the
face. Figure 3 A shows the five most abundant air–water interface.
hydration structures formed between Criegee inter-
mediates and interfacial water molecules. For a Crie-
gee–water reaction to happen, both O2 and C1 atoms
of Criegee intermediate should interact with water
molecules. The Complex 4 and 5 (Figure 3) meet
these requirements. The total percentage of Com-
plex 4 and 5 for CH2OO, anti-CH3CHOO, and syn-
CH3CHOO are 40.23 %, 38.74 %, and 22.93 %,
respectively. (This analysis for CH2O2 at air–water
interface is based on the trajectories before the
occurrence of reactions from four independent sim-
ulations). The least tendency of syn-CH3CHOO to Figure 3. A) Five typical configurations of anti-CH3CHOO–H2O complex. Com-
form the favorable complexes is due to the location of plex 1 corresponds to the no interaction with water molecule configuration.
a syn methyl substituent and its strong hydrophobic- Complex 2 corresponds to interaction of the terminal Criegee oxygen atom with
ity. As shown in Figures S2 A and S2 B, the strong an interfacial water molecule (O2···Hw < 1.75 b). Complex 3 corresponds to
hydrophobicity of methyl substituent repels the interaction of the Criegee carbon atom with an interfacial water molecule
interfacial water molecules away from the syn- (C1···Ow < 2.8 b). Complex 4 corresponds to interaction of the terminal oxygen
and carbon atoms of the Criegee moiety with interfacial water molecules
CH3CHOO. As a result, few water molecules are
(O2···Hw and C1···Ow). Complex 5 is similar to Complex 4 except that two
able to interact with C1 atom of syn-CH3CHOO. interfacial water molecules interact with the terminal Criegee oxygen atom.
Because the C1··water interaction plays more crucial B) Average probabilities of different complex configurations.
roles in the Criegee–water reaction than the
O2···water one (see explanation in Figure S3), the
reactivity of syn-CH3CHOO would decrease due to the lesser
hydration of C1 atom.
The total percentage of Complex 4 and 5 for anti-
CH3CHOO is almost the same with that of CH2OO. Despite
that, both display totally different reactivity at the air–water
interface. To gain deeper insights into this differential
behavior, we examined the orientation of Criegee intermedi-
ates on the water surface by calculating the angular distribu-
tion function. The angle theta (q) is the angle between the C1-
O1-O2 plane and the vector of C1 and the center of mass of
the water droplet, as illustrated in Figure 4 A. Figure 4 B
Figure 4. A) A schematic representation of the orientation of CH2OO
shows the angle distribution profiles for C1 and C2 Criegee and anti-CH3CHOO on the water droplet. B) Computed angular
intermediates. The q for CH2OO is found distributed around distribution function of CH2OO, anti-, and syn-CH3CHOO Criegee
7088, which indicates that CH2OO almost lies flat on the water intermediates on the water droplet.

7742 www.angewandte.org T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2017, 56, 7740 –7744

Communications
surface. By contrast, the q of anti-CH3CHOO is
distributed around 2088, suggesting that anti-
CH3CHOO tends to penetrate vertically into the
aqueous and project the methyl substituent out of the
water droplet. Such an orientation of anti-CH3CHOO
would pull atom C1 away from the water-droplet
surface.
The less hydration of the C1 atom in syn-
CH3CHOO or its projection in anti-CH3CHOO
away from the interfacial water at the aqueous
interface would make the water molecules that
interact with C1 atom less solvated. Figure 5 shows
the radial distribution function of OC (O atom in
water interacting with C1 atom) with other Ow atoms
in the water droplet. The OC (interacting with
CH2OO) is much more hydrated by surrounding
water molecules. The strong hydration layer was
shown to be crucial in lowering the proton dissocia-
tion barrier and facilitating the proton dissociation.[14]
As a result, the proton bonded to OC atom in CH2OO
reaction can easily dissociate by the surrounding
strong hydration layer. For both syn- and anti-
CH3CHOO, the weak hydration layer formed by OC
atom hampers the dissociation of the proton bonded
to OC atom, which makes CH3CHOO inert towards
water at the air–water interface.
Figure 5. A) An illustration of the interaction of OC (O atom in water
interacting with C1 atom) with other Ow atoms in the water droplet.
B) Computed radial distribution function of OC atom with other Ow
atoms in the water droplet.
Next, we calculated the probability for the loop structures
involving Criegee intermediate and interfacial water mole-
cules (Figure 6 A). As depicted in Figure 6 B, the loop
structure of CH2OO with water dimer on the droplet surface
has the highest probability. This is consistent with the recent
QM/MM simulation results that the water dimer-mediated
proton-transfer reaction accounts for the highest percentage
among all the reaction pathways.[14] However, for both syn-
and anti-CH3CHOO, the loop structure with interfacial water
at the droplet surface is hardly seen.
Furthermore, the dynamic stability of loop structures is
investigated by computing the correlation function C(t). The
correlation function C(t) of the loop structure is given by
[Eq. (1)]:
Angew. Chem. Int. Ed. 2017, 56, 7740 –7744 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Chemie
Figure 6. A) A schematic representation of loop structures formed by Criegee
intermediates with interfacial water molecules. B) The probability of loop
structures with different number of water molecules. C) The correlation function
of loop structures with two water molecules. D) The correlation function of loop
structures with three water molecules.
1 X N S1
hCðtÞi ¼ h ½h ð0Þhi ðtÞAi ð1Þ
N S1 i¼1 i
where NS1 is the loop structure number, hi(t) is 1 or 0 for
a loop structure formed or broken at time t.
Figure 6 C,D show the correlation function for the loop
structures formed by Criegee intermediates with water dimer
and water trimer, respectively. The half lifetime of these loop
structures is found on the order of a few femtoseconds.
Interestingly, the decay rate of the loop structures involving
CH3CHOO is higher than that formed by CH2OO, which
indicates the syn- and anti-CH3CHOO forms less stable loop
structure with water molecules on the aqueous surface. These
results suggest that the strong hydrophobicity of methyl
substituent hampers the formation of the necessary pre-
reaction complex for the Criegee-interfacial water reaction.
To further verify the role of hydrophobicity in impacting
the Criegee reactivity at the aqueous surface, we examined
the adsorption behavior of larger (CH3)2COO, syn- and anti-
CH2C(CH3)CHOO at air–water interface. The latter two
Criegee intermediates are produced by isoprene ozonolysis
and should help us generalizing our results to the Criegee
chemistry occurring in the forested environments. No water
reaction is observed for any of the larger Criegee intermedi-
ates over the BOMD time scale of 34 ps and 56 ps (see
Figure S4, Movies S6 to S8), which indicates the strong
hydrophobicity of substituents could be a ubiquitous reac-
tivity determinant for Criegee intermediates at the air–water
interface.
In conclusion, we have performed BOMD simulations to
examine the substituent effects on the reactivity of Criegee
intermediates at the air–water interface. The results show that
unlike CH2OO, both syn- and anti-CH3CHOO remain inert
www.angewandte.org 7743

Communications
towards water at the air–water interface. The strong hydro-
phobicity of methyl substituent renders both syn- and anti-
CH3CHOO only weakly hydrated at the air–water interface,
hampering the CH3CHOO–water reaction. Additional simu-
lations with larger Criegee intermediates further suggest that
the strong hydrophobicity of substituents plays a crucial role
in determining the reactivity of Criegee intermediates on the
water droplet surface. An important implication of these
results is that the Criegee intermediates with hydrophobic
substituents (> C1) in the troposphere can have much longer
life time than CH2OO at water interfaces, and thus at the
interface, reactions with other gas-phase atmospheric trace
gases, such as SO2, organic or inorganic acids may become
important.
Acknowledgements
This work is supported by the National Science Foundation
(CHE-1500217), a fund from Beijing Advanced Innovation
Center for Soft Matter Science & Engineering for summer
visiting scholar, and by the University of Nebraska Holland
Computing Center.
Conflict of interest
The authors declare no conflict of interest.
Keywords: ab initio dynamics simulation · air–water interface ·
atmospheric chemistry · Criegee intermediate
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Manuscript received: March 15, 2017
Version of record online: May 4, 2017
Angew. Chem. Int. Ed. 2017, 56, 7740 –7744