Identification of the early intermediates formed in ozonolysis of: Cis-2-butene and limonene: A theoretical and matrix isolation study

Article abstract of DOI:10.1039/c9ra04176a

This study combined quantum chemical calculations and the matrix isolation technique to identify the formation of primary intermediates from the ozonolysis of cis-2-butene and limonene. Quantum chemical calculations were conducted under the framework of density functional theory (DFT) at M06-2x/6-311+(d, p) level of theory to predict the possible mechanism as well as the new absorption bands. New bands whose intensity increased with annealing, were observed in twin jet deposition, which indicated the formation of primary ozonides, CI and secondary ozonides in the investigated systems. Isotopic labeling (¹⁸O) experiments further supported the assignment of observed bands. The results and findings in this study would enrich the understanding of the reaction mechanism of alkene ozonolysis.

Full text of DOI:10.1039/c9ra04176a

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Identification of the early intermediates formed in
ozonolysis of cis-2-butene and limonene:
a theoretical and matrix isolation study†
a
Cite this: RSC Adv., 2019, 9, 20100
Shan-shan Li,a Xiao-yang Yang,b Yi-sheng Xub and Lei Jiang
*
This study combined quantum chemical calculations and the matrix isolation technique to identify the
formation of primary intermediates from the ozonolysis of cis-2-butene and limonene. Quantum
chemical calculations were conducted under the framework of density functional theory (DFT) at M06-
2x/6-311+(d, p) level of theory to predict the possible mechanism as well as the new absorption bands.
New bands whose intensity increased with annealing, were observed in twin jet deposition, which
indicated the formation of primary ozonides, CI and secondary ozonides in the investigated systems.
Isotopic labeling (18O) experiments further supported the assignment of observed bands. The results and
findings in this study would enrich the understanding of the reaction mechanism of alkene ozonolysis.
Received 3rd June 2019
Accepted 20th June 2019
DOI: 10.1039/c9ra04176a
rsc.li/rsc-advances
CCN.8 Limonene is recognized as the second major terpene
emitted by natural source in the atmosphere,9–12 and the
1. Introduction
oxygenated products of limonene ozonolysis could contribute to
SOA formation as those of pinene ozonolysis do.8,11
Ozone readily reacts with alkenes through association with
C]C double bonds. Aldehydes and/or ketones, organic acids as
well as other fragmentation products are ultimately produced
following the cleavage of the C]C double bond in alkenes. The
widely accepted ozonolysis mechanism was originally proposed
by Criegee.1 The initial step involves a highly exothermic
concerted 1,3-dipolar cyclo-addition of ozone to the C]C
double bond forming primary ozonide (POZ) with the 1,2,3-
trioxolane ring. Second, the POZ with excess energy would
undergo rapid decomposition of the trioxolane ring to produce
a primary carbonyl and a highly reactive carbonyl oxide inter-
mediate referred to as the Criegee intermediate (CI). The CI can
react unimolecularly, be stabilized by collisions with the
surrounding molecules or recombine with the produced
carbonyl to produce the more stable secondary ozonide (SOZ)
with the 1,2,4-trioxolane ring.2,3 Since the contribution of
secondary organic aerosol (SOA) formation from vastly emitted
biogenical compounds to aerosol loading was proposed in
1960,4 the ozonolysis of monoterpenes has drawn great atten-
tion because these reactions may promote the formation of
urban SOAs.5 When emitted to the atmosphere, monoterpenes
may participate in SOA formation6,7 due partly to their reactions
with O3 leading to water-soluble products, which can act as
Experimental and theoretical researchers have focused on
product determination and thermodynamic/kinetic parameter
evaluation of limonene ozonolysis.9–16 The rate constant of
limonene ozonolysis was measured to be 2.1 ꢀ 0.15 ꢁ 10ꢂ18 cm3
per molecule per second based on relative rate techniques by
Khamaganov et al.,10 which well corresponded with the previous
experimental results obtained by Shu et al.13 The major products
including limonic acid, keto-limonene, limononaldehyde, and
limononic acid were identied by several groups.10,11,14 Recently
Jiang et al.15 and Ayadi et al.16 attempted to reveal the mecha-
nism of limonene ozonolysis using theoretical methods, and
the major reaction pathway with branching ratio was proposed.
Despite these efforts, the formed CIs from limonene ozonolysis
are not veried in detail, which impedes the unambiguous
explanation of the mechanism for limonene ozonolysis. This
can be partly attributed to the shortcomings of current experi-
mental instruments on detecting the short-lived substances.
Currently, matrix isolation17,18 has been becoming one of the
most popular techniques to investigate short-lived
substances19–25 including CIs.20,21,24 In the matrix isolation
system, the concerned reaction systems are trapped in argon
matrix at temperatures lower to ꢃ14 K, allowing for very short
mixing time. Thus, the short-lived substances can be isolated
and stabilized by the matrix molecules around. The infrared
spectroscopy conducted under matrix isolation can provide
reliable characterization of CIs and has been applied extensively
in the exploration addressing alkene ozonolysis. Hoops et al.
observed the CIs formed in the ozonolysis of cyclopentadiene
and cyclopentene by matrix isolation.21 Clay et al. studied the
aBeijing Municipal Research Institute of Environmental Protection, Beijing 100037,
China. E-mail: 154249704@qq.com; jiangle3657@sina.com; Fax: +86-10-68314675
bState Key Laboratory of Environmental Criteria and Risk Assessment, Chinese
Research Academy of Environmental Sciences, Beijing 100012, China. E-mail: xuys@
craes.org.cn; yangxy@craes.org.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c9ra04176a
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mechanism of the ozonolysis of cis-2-butene by matrix isolation equipped to the vacuum vessel, which was located at the sample
and successfully detected CIs.22 However, the standard infrared beam of the FTIR spectrometer (Vertex 80v, Bruker) for the
spectra of CIs are rarely reported, which exacerbated the diffi- duration of the experiment. The spectra were recorded from 400
culty of CI recognition and mechanism validation. Meanwhile, to 4000 cmꢂ1 averaging 32 scans at a resolution of 0.5 cmꢂ1
.
quantum chemical calculation has been widely used to explore Aer the 14 K spectrum was recorded, the temperature in the
the reaction mechanisms and analyze the reaction products, chamber was raised to 35 K, which was maintained for 30 min
which provides additional evidence to overcome the short- to permit diffusion and/or reaction, and the 35 K spectrum was
comings of matrix isolation infrared spectroscopy.25
recorded aer the chamber was cooled down again to 14 K. The
In this study, we combined quantum chemical calculation data were analyzed by OPUS 7.2 soware. The experiments were
and matrix isolation infrared spectroscopy to conrm CI triplicated to ensure the reproducibility.
formation and reveal the mechanism of the ozonolysis of cis-2-
butene and limonene. The possible reaction pathways, the
corresponding rate constants, and spectroscopic information
All theoretical calculations in this paper were performed by
were predicted by quantum chemical calculations, which were
2.4. Computational methods
Gaussian 09.26 Geometry optimizations and vibrational calcula-
tions were carried out under the framework of density functional
theory (DFT) at M06-2x/6-311+(d, p) level of theory.27 The optimized
structures were determined to be minima with no imaginary
frequency or to be transition states with one imaginary frequency
by vibrational calculations, and all vibrational frequencies are
scaled by 0.944.28 The potential energy surface was constructed at
CCSD(T)/6-311+(d, p)//M06-2x/6-311+(d, p) level of theory. The
KiSThelP soware29 was employed to calculate the rate constants
of the concerned elementary steps based on TST theory.
further veried by matrix isolation infrared spectroscopy. 18O
isotope labeling was utilized to additionally characterize the
early intermediates. cis-2-Butene was selected to validate the
reliability of our experimental and theoretical methods, and
provided fundamental understanding to the study on limonene
ozonolysis.
2. Materials and methods
2.1. Chemicals
Limonene (99.0%, TCI Shanghai, China), cis-2-butene (99.0%,
Deyang, China), 1-methyl-1-cyclohexene (98.0%, TCI Shanghai,
China) and 1-methyl-1,4-cyclohexadiene (97.0%, Alfa Aesar,
China) were used without any further purication. O3 and 18O3
were produced by Tesla coil discharge of O2 (99.999%, Deyang,
China) and 18O2 (99.5%, Shanghai Research Institute of
Chemical Industry, China), respectively, and then trapped at 77
K to wipe off residual O2 and trace gases. Argon (99.999%,
Deyang, China) was selected as the matrix gas to dilute the
samples in all the experiments. The argon/sample ratios were
all adjusted to be 200/1.
3. Results and discussion
3.1. Ozonolysis of cis-2-butene
3.1.1 Theoretical predicted mechanism. Fig. 1 and S1†
interpret the mechanism of cis-2-butene ozonolysis and the
corresponding potential energy surface (PES), respectively. A
van der Waals complex (Vdw) with the binding energy of
ꢂ2.11 kcal molꢂ1 forms when cis-2-butene interacts with ozone.
Then, primary ozonide (POZ) can be produced from Vdw via
a transition state. The formation of POZ is exothermic by
53.67 kcal molꢂ1 with a low potential barrier of 2.37 kcal molꢂ1
.
The C–C bond and O–O bond in POZ can elongate and nally
break, leading to aldehyde and Criegee intermediate (CI). POZ
formation, POZ decomposition and SOZ formation is
exothermic with low or moderate potential barriers. The
production of CI is exothermic by 23.60 kcal molꢂ1 with
a moderate potential barrier of 13.58 kcal molꢂ1. The formation
of SOZ is exothermic by 44.58 kcal molꢂ1, implying that SOZ is
relatively stable and, therefore, could be detected more easily
than CI. The optimized molecular structures of the involved
substances in Fig. 1 are shown in Fig. S2.†
2.2. Blank experiments
Prior to each co-deposition experiment, blank experiments
including deposition and annealing were conducted on all of
the parent compounds. The obtained blanks were used as
authentic spectra of the pure parent compounds, which
provided unambiguous identication of product bands and the
baseline for the extent of the reactions.
2.3. Ozonolysis experiments
All the experiments were conducted on a matrix isolation
3.1.2 Spectra. Twin jet mode allowing for short reaction
apparatus. The low temperature (ꢃ14 K) was obtained by time was employed in this study. In the twin jet experiment,
a closed-cycle helium compressor-cooled cryostat (PT-SHI-4-5, a sample of Ar/cis-2-butene ¼ 200 was co-deposited with
Janis Research Company, USA) in a vacuum chamber. The a sample of Ar/ozone ¼ 200. As illustrated in Fig. 2, some new
pressure inside the cryostat chamber was monitored by a pres- bands were recorded in the initial 14 K spectrum of the
sure gauge (WRG-NW25, Edward, UK). A base pressure of (2–5) deposited matrix during the short condensation time, indi-
ꢁ 10ꢂ5 mbar was recorded at the initial stage of each experi- cating that a rapid reaction occurred when co-depositing cis-2-
ment. The deposition process was performed as twin jet mode, butene and ozone into Ar matrices. Subsequently, this sample
that is, the Ar/O3 and Ar/sample mixtures were inputted into the was annealed to 35 K and recooled to 14 K and an annealed
cold window through two separate nozzles in the cold head, spectrum recorded. New bands at 720, 890, 920, 1062, 1115,
which lasted for ꢃ210 min at ꢃ5 mmol hꢂ1. ZnSe windows were 1144, 1341, 1470 and 1720 cmꢂ1 were observed. The intensities
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Fig. 1 The mechanism of cis-2-butene ozonolysis embedded with the energy barrier DE and reaction energy DH (all in kcal molꢂ1, 298.15 K).
Geometries of the stationary points involved in the stabCI–OO + H2O reaction obtained at the M06-2x/6-311+G(d, p) level of theory. Bond
lengths and intermolecular distances are given in A˚.
of the bands appeared at 930, 1039, 1105, 1158, 1231, 1341, 1578
For CI, only one vibrational mode for the antisymmetric
and 1639 cmꢂ1 decreased as annealing, indicating that these stretch of the C–O–O linkage has signicant intensity (i.e., I > 40
bands were produced by the complexed reactants. Similar twin km molꢂ1), which is predicted by DFT calculations. This mode
jet experiment was run with the samples of Ar/cis-2-butene ¼ has a predicted 18O shi of ꢂ22 cmꢂ1. The 920 cmꢂ1 band
200 and Ar/18O3 ¼ 200. 18O counterparts of the product bands recorded in the experiment is in reasonable agreement with the
were observed at 692, 875, 904, 1059, 1102, 1138, 1340, 1470, calculated results, and shows an 18O shi of ꢂ18 cmꢂ1. Some
and 1690 cmꢂ1, which were shown in Fig. S3.† Upon annealing, previous matrix isolation studies also reported that the char-
these bands grew substantially, just opposed to their 16O acteristic absorption band of different CIs were at 920–
counterparts. However, interpretation of this phenomenon 980 cmꢂ1
could not be accurately provided at this time. The new product of the 920 cmꢂ1 band upon annealing. The concurrent growth
bands and their assignments are summarized in Table 1.
of the band at 1720 cmꢂ1 suggests the formation of acetalde-
.
21,22,30,31 The band at 1720 cmꢂ1 grew with the increase
DFT calculations predict that the two major vibrational hyde, since CI and acetaldehyde were produced simultaneously
modes for POZ are at 703 and 1048 cmꢂ1, which are generally and should be trapped in the same matrix cage. Moreover, the
consistent with the two observed experimental bands at 720 and experimental 18O shi of the 1720 cmꢂ1 band is 39 cmꢂ1, closely
1062 cmꢂ1. The band at 720 cmꢂ1 shied for 28 cmꢂ1 when 18O3 matching the theoretically anticipated shi for acetaldehyde.
was employed, which agreed with the predicted 18O shi of The bands at 890, 1115, 1144, 1340, and 1470 cmꢂ1 in this study
32 cmꢂ1. The symmetric stretching mode of C–O ring in POZ are assigned to the secondary ozonide (SOZ) of cis-2-butene. The
was calculated to be at 1048 cmꢂ1, near the band at 1062 cmꢂ1
This band was theoretically predicted to have an 8 cmꢂ1 18
.
O
890 and 1144 cmꢂ1 bands exhibit obvious isotopic shi. No 18
shi was recorded for the bands at 1340 and 1471 cmꢂ1, which
O
shi, in comparison with the 3 cmꢂ1 shi that was experi- were assigned to CH2 bending modes. As shown in Table 1,
mentally recorded. Given that the 18O3 used in our experiments vibrational modes of the SOZ predicted by theoretical calcula-
inevitably mixed with minor part of 16O3, the isotopic shi tions are in reasonable agreement with the experimental bands,
observed should be in the range of 0 and the theoretical pre- and the calculated isotopic shi of each vibrational mode for
dicted values, and the product bands observed in 18O3 experi- the 18O isotopomer is close to the observed shi. This well
ments were thus broader (sometimes with no well-resolved matches the research by Clay et al.22 and validates our experi-
band position).
mental procedures.
Fig. 2 Infrared spectra of the co-deposition of the samples of Ar/cis-2-butene ¼ 200 and Ar/O3 ¼ 200. The blue line (middle) indicates initial
deposition at 14 K and the purple line (top) represents the spectrum after annealing to 35 K, compared to a blank spectrum of Ar/cis-2-butene ¼
200 (red, bottom).
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Table 1 Product band positions and assignments in the ozonolysis of Table 2 The calculated rate constants (298.15 K) of the elementary
cis-2-butene (in cmꢂ1
)
reactions involved in limonene ozonolysis
Experimental
Calculated position
Elementary reactions
Rate constanta
position and shis
and shis
Limonene + ozone /
POZ1
POZ1 / CI1
POZ1 / CI2
Limonene + ozone /
POZ2
1.90 ꢁ 10ꢂ15
16O
D
18O
16O
703
D
18O
Assignment
1.16 ꢁ 10ꢂ8
1.22 ꢁ 10ꢂ2
1.79 ꢁ 10ꢂ16
720
890
920
1062
1115
1144
1340
1470
1720
ꢂ28
ꢂ18
ꢂ18
ꢂ3
ꢂ13
—
0
0
ꢂ39
ꢂ32
POZ
SOZ
CI
POZ
SOZ
SOZ
SOZ
SOZ
912
1048
ꢂ22
ꢂ8
POZ2 / CI3
POZ2 / CI4
1.44 ꢁ 10ꢂ4
1.49 ꢁ 10ꢂ7
a
The rate constants of unimolecular reaction are in sꢂ1, while the rate
constant of bimolecular reaction are in cm3 per molecule per second.
1761
ꢂ37
Acetaldehyde
formation of POZ1 is much faster than that of POZ2 by a factor
of ꢃ9, as shown in Table 2. The reactions associated with POZ1
are therefore considered to be more important in comparison of
the reactions related to POZ2. Because POZ1 is asymmetric, the
–OOO– ring in POZ1 can be opened by two pathways to produce
CI1 and CI2. The potential barrier of CI1 formation is
17.72 kcal molꢂ1, which is 7.63 kcal molꢂ1 higher than that of
CI2 formation. Moreover, the rate constant of CI2 formation is
ꢃ6 orders of magnitude larger than that of CI1 formation.
Therefore CI2 formation is predominant over CI1 formation,
and the subsequent reactions of CI1 are not further discussed.
Analogously, POZ2 can produce CI3 and CI4 through the
rupture of –OOO– ring. The formation of CI3 is anticipated to be
3.2. Ozonolysis of limonene
3.2.1 Theoretical predicted mechanism. The mechanism of
limonene ozonolysis and corresponding PES are shown in Fig. 3
and S4,† respectively. Ozone can interact with the C]C double
bond within the carbon ring of the limonene molecule to
produce Vdw1, or interact with the C]C double bond within
the side chain, leading to Vdw2. The formation of Vdw1 is more
favorable than that of Vdw2. The formation of both POZs from
the corresponding van der Waals complexes is highly
exothermic of ꢃ50 kcal molꢂ1 with low potential barriers.
However, the rate constant calculations suggest that the
Fig. 3 The mechanism limonene ozonolysis embedded with the potential energy DE and reaction energy DH (all in kcal molꢂ1, 298.15 K).
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Table 3 Product band positions and assignments in the ozonolysis of
much favorable than that of CI4 by judging the corresponding
potential barrier and rate constant. The optimized molecular
structures of the involved substances in Fig. 3 are shown in
Fig. S5 and S6.†
limonene (in cmꢂ1
)
Experimental
Calculated
position and shis
position and shis
3.2.2 Spectra. The sample of Ar/limonene ¼ 200 was co-
deposited with a sample of Ar/ozone ¼ 200 in the twin jet
experiment. Fig. 4 illustrates that new absorption bands were
more obvious when this sample was subsequently annealed to
35 K. New bands at 656, 930, 945, ꢃ1050, ꢃ1070, 1151, ꢃ1232,
1720, 1758, ꢃ1850 and 2147 cmꢂ1 were observed. The bands at
ꢃ1050, ꢃ1070, ꢃ1232 and ꢃ1850 were broad with no well-
resolved peak, which suffered from the interference with limo-
nene and ozone as well. Similar twin jet deposition experiment
was run with the samples of Ar/limonene ¼ 200 and Ar/18O3 ¼
200. The spectra obtained using 18O isotope was only provided
in the ESI† as reference. The new product bands and their
assignments are summarized in Table 3.
POZ, CI and SOZ are potential and reasonable intermediates
produced by limonene ozonolysis. Nevertheless, the identica-
tion of these intermediates through clear assignments of the
absorption bands is nontrivial. The assignments could be ach-
ieved by comparing the vibrations and their corresponding
isotopic shis obtained from experimental and theoretical
results (Table 3). Given that some bands overlapped with reac-
tant bands or other product bands, quantitative conclusion
could not be reached for these product bands. Nonetheless, the
bands at 656, 930, 945, ꢃ1050, ꢃ1070, 1151, ꢃ1232 and
1720 cmꢂ1 could be reasonably assigned to POZ, CI and SOZ in
the light of position and isotopic shis. Generally, the bands
assigned to POZ, CI and SOZ are in reasonable agreement with
the theoretical calculations.
16O
656
D
18O
16O
D
18O
Assignment
ꢂ15
651
885
925
944
968
ꢂ12
SOZ1
POZ2
CI2
930
945
ꢂ17
ꢂ11
ꢂ20
ꢂ15
CI3
SOZ2
SOZ1
SOZ2
SOZ1
POZ2
SOZ2
POZ1
SOZ1
POZ1
SOZ2
POZ2
SOZ2
POZ1
SOZ1
SOZ1
SOZ1
Formaldehyde
970
ꢃ1050
ꢃ1070
ꢂ3
ꢂ6
1051
1054
1072
1075
1078
1087
1102
1125
1149
1167
1186
1195
1226
1273
1732
ꢂ8
ꢂ9
ꢂ8
ꢂ10
ꢂ8
1151
ꢂ15
ꢂ12
ꢃ1232
ꢂ19
ꢂ28
ꢂ22
ꢂ31
1720
944 cmꢂ1, respectively. The 926 cmꢂ1 and 945 cmꢂ1 bands
observed in the experiment matches well with the calculated
results. The intensity of the 945 cmꢂ1 band is much stronger
than that of 926 cmꢂ1, suggesting that CI2 is the major CI in
limonene ozonolysis. This agrees with our theoretical predic-
tion. Some previous matrix isolation study also reported that
CI2/CI3 is calculated to have only one vibrational mode with
signicant intensity belonging to the antisymmetric stretch of
the C–O–O linkage. The calculated vibrational frequencies of
the C–O–O stretching mode of CI2 and CI3 are 930 and
the characteristic absorption band of different CIs were at 920–
980 cmꢂ1
,
which was in good agreement with the
21,22,30,31
observations here.
Fig. 4 Infrared spectra of the co-deposition of the samples of Ar/limonene ¼ 200 and Ar/O3 ¼ 200. The blue line (middle) indicates initial
deposition at 14 K and the purple line (top) represents the spectrum after annealing to 35 K, compared to a blank spectrum of Ar/limonene ¼ 200
(red, bottom).
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Oxidation of a-Pinene and Limonene, J. Aerosol Sci., 2007,
38, 843–852.
4. Conclusions
9 J. Kesselmeier and M. J. Staudt, Biogenic Volatile Organic
Compounds (VOC): An Overview on Emission, Physiology
and Ecology, Atmos. Chem., 1999, 33, 23–88.
10 V. G. Khamaganov and R. A. Hites, Rate Constants for the
Gas-Phase Reactions of Ozone with Isoprene, a- and b-
Pinene, and Limonene as a Function of Temperature, J.
Phys. Chem. A, 2001, 105, 815–822.
11 S. Leungsakul, M. Jaoui and R. M. Kamens, Kinetic
Mechanism for Predicting Secondary Organic Aerosol
Formation From the Reaction of d-Limonene with Ozone,
Environ. Sci. Technol., 2005, 39, 9583–9594.
In this study, the early intermediate products formed during
ozonolysis of cis-2-butene and limonene were proposed by
quantum chemical calculations, which was veried by matrix
isolation infrared spectroscopy. Primary ozonides, Criegee
intermediates, and secondary ozonides were identied by
comparing the vibrations and their corresponding isotopic
shis obtained from experimental and theoretical results. The
ozonolysis of limonene follows the Criegee mechanism, and the
dominant pathways in these reactions was revealed. The results
and ndings in this study would provide theoretical and
experimental support for the mechanism of ozonolysis of
alkenes.
´
´
12 V. M. Ramırez-Ramırez and I. Nebot-Gil, Theoretical Study of
the OH Addition to the Endocyclic and Exocyclic Double
Bonds of the d-Limonene, Chem. Phys. Lett., 2005, 409, 23–
28.
Conflicts of interest
13 Y. Shu and R. Atkinson, Rate Constants for the Gas-phase
Reactions of O3 with a Series of Terpenes and OH radical
Formation From the O3 reactions with Sesquiterpenes at
296 ꢀ 2 K, Int. J. Chem. Kinet., 1994, 26, 1193–1205.
14 J. Zhang, K. E. H. Hartz, S. N. Pandis and N. M. Donahue,
Secondary Organic Aerosol Formation from Limonene
Ozonolysis: Homogeneous and Heterogeneous Inuences
as a Function of NOx, J. Phys. Chem. A, 2006, 110, 11053–
11063.
All the authors declare no conict of interest.
Acknowledgements
This work was nancially supported by the National Science
Foundation for Young Scientists of China (Grant No. 41405120)
and National Natural Science Foundation of China (Grant No.
21607093 and No. 41375133).
15 L. Jiang, W. Wang and Y. Xu, Ab initio Investigation of O3
addition to Double Bonds of Limonene, Chem. Phys., 2010,
368, 108–112.
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