Synthesis, Electronic Spectroscopy, and Photochemistry of Methacrolein Oxide: A Four-Carbon Unsaturated Criegee Intermediate from Isoprene Ozonolysis

Article abstract of DOI:10.1021/jacs.9b05193

Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the earth's atmosphere, generates the four-carbon unsaturated methacrolein oxide (MACR-oxide) Criegee intermediate. The first laboratory synthesis and direct detection of MACR-oxide is achieved through reaction of photolytically generated, resonance-stabilized iodoalkene radicals with oxygen. MACR-oxide is characterized on its first π? a? πelectronic transition using a ground-state depletion method. MACR-oxide exhibits a broad UV-visible spectrum peaked at 380 nm with weak oscillatory structure at long wavelengths ascribed to vibrational resonances. Complementary theory predicts two strong ?€? a? πtransitions arising from extended conjugation across MACR-oxide with overlapping contributions from its four conformers. Electronic promotion to the 1¹π? state agrees well with experiment, and results in nonadiabatic coupling and prompt release of O ¹D products observed as anisotropic velocity-map images. This UV-visible detection scheme will enable study of its unimolecular and bimolecular reactions under thermal conditions of relevance to the atmosphere.

Full text of DOI:10.1021/jacs.9b05193

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Article
Synthesis, electronic spectroscopy and photochemistry
of methacrolein oxide: A four carbon unsaturated
Criegee intermediate from isoprene ozonolysis
Michael F Vansco, Barbara Marchetti, Nisalak Trongsiriwat, Trisha Bhagde,
Guanghan Wang, Patrick J Walsh, Stephen J Klippenstein, and Marsha I. Lester
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05193 • Publication Date (Web): 26 Aug 2019
Downloaded from pubs.acs.org on August 26, 2019
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Synthesis, electronic spectroscopy and photochemistry
of methacrolein oxide: A four carbon unsaturated Criegee
intermediate from isoprene ozonolysis
Michael F. Vansco1, Barbara Marchetti1, Nisalak Trongsiriwat1, Trisha Bhagde1,
Guanghan Wang1, Patrick J. Walsh1,* Stephen J. Klippenstein2, and Marsha I. Lester1,*
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1 Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323
2 Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439
ABSTRACT: Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the Earth’s atmosphere,
generates the four-carbon unsaturated methacrolein oxide (MACR-oxide) Criegee intermediate. The first laboratory
synthesis and direct detection of MACR-oxide is achieved through reaction of photolytically generated, resonance-stabilized
iodoalkene radicals with oxygen. MACR-oxide is characterized on its first * electronic transition using a ground state
depletion method. MACR-oxide exhibits a broad UV-visible spectrum peaked at 380 nm with weak oscillatory structure at
long wavelengths ascribed to vibrational resonances. Complementary theory predicts two strong * transitions arising
from extended conjugation across MACR-oxide with overlapping contributions from its four conformers. Electronic
promotion to the 11* state agrees well with experiment, and results in nonadiabatic coupling and prompt release of O 1D
products observed as anisotropic velocity map images. This UV-visible detection scheme will enable study of its
unimolecular and bimolecular reactions under thermal conditions of relevance to the atmosphere.
1. Introduction
Isoprene (2-methyl-1,3-butadiene) is the most abundant nonmethane volatile organic compound in the Earth’s
troposphere with emissions approaching 600 Tg per year.1 The primary source of isoprene is foliar emission (> 90%),
while its removal is controlled by oxidation reactions initiated by hydroxyl radicals (OH), ozone (O3), and nitrate radicals
(NO3).2-4 Ozonolysis accounts for ca. 10% of atmospheric isoprene loss and occurs with a relatively slow rate coefficient
of 1.19 x 10-17 cm3 molecule-1 s-1.5-6 Critical reaction intermediates arising from isoprene ozonolysis are the focus of the
present study.
Ozonolysis of isoprene proceeds by cycloaddition of ozone across one of the two C=C bonds to form two distinct
primary ozonides (POZ) as depicted in Scheme 1. The two POZ promptly decompose via highly exothermic reactions to
form carbonyl and zwitterionic carbonyl oxide products, the latter known as Criegee intermediates. Ozonolysis at the
C(1)=C(2) bond results in a POZ that generates methyl vinyl ketone oxide ((CH2=CH)(CH3)COO, MVK-oxide) with
formaldehyde (CH2O) or formaldehyde oxide (CH2OO) with methyl vinyl ketone ((CH2=CH)(CH3)CO, MVK).
Ozonolysis at the C(3)=C(4) bond results in a POZ that generates methacrolein oxide ((CH2=C(CH3))CHOO, MACR-oxide)
with formaldehyde or CH2OO with methacrolein ((CH2=C(CH3))CHO, MACR).5, 7-9 The overall branching of Criegee
intermediates from isoprene ozonolysis is estimated to be 58% CH2OO, 23% MVK-oxide, and 19% MACR-oxide.5, 10
Given the importance of isoprene ozonolysis, it is remarkable that very little is known about the two four-carbon
unsaturated Criegee intermediates MVK-oxide and MACR-oxide.11 In contrast, there has been extensive spectroscopic
characterization of CH2OO and its bimolecular reactions with key atmospheric species.12-16 This paper presents the first
laboratory synthesis and direct observation of MACR-oxide by UV-vis spectroscopy. The experimental results are
complemented by theoretical predictions of the strong * electronic transitions of MACR-oxide and resultant
dissociation pathways. This study builds on recent reports from this laboratory of IR action and UV-vis depletion spectra
of MVK-oxide.17-18 MACR-oxide cannot be detected by an analogous IR action spectroscopy technique because OH
radicals are not a significant reaction product. Various unimolecular decay processes and bimolecular reactions of MVK-
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oxide and MACR-oxide with atmospheric species (e.g. water vapor, SO2, NOx, and organic acids) are expected to yield a
wide range of products,14-15, 19-20 including aerosols that effect climate.21
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Scheme 1. Criegee intermediates and carbonyl co-products formed in ozonolysis of isoprene.
The four-carbon unsaturated MVK-oxide and MACR-oxide intermediates are predicted to be distinctly different than
previously investigated saturated carbonyl oxides including CH2OO and alkyl-substituted Criegee intermediates.22-24 In
contrast to the four  electron system of saturated carbonyl oxides, both MVK-oxide and MACR-oxide have extended -
conjugation involving six  electrons across the vinyl (CH2=C) and carbonyl oxide (C=O+O) functional groups.25-26 The
extended  conjugation is expected to fundamentally change the electronic properties of unsaturated Criegee
intermediates,8-9 and potentially their unimolecular and bimolecular chemistry in the atmosphere. MVK-oxide and
MACR-oxide are isomers, both having vinyl and methyl substituents, but differ in the position of the methyl group.
MVK-oxide and MACR-oxide are each predicted to have four distinct conformers with similar ground state energies
(within ca. 3.2 kcal mol-1), yet have significant barriers to rotation that restrict interconversion between the conformers.8-9,
17
In MACR-oxide, the four conformers differ in the relative orientation of the terminal O atom with respect to the
methine H atom (syn vs. anti) and in the relative orientation of the C=C and C=O bonds (cis vs. trans), as depicted in
Figure 1. In isoprene ozonolysis, the distribution of syn/anti conformers of MACR-oxide are predicted to be asymmetric
with 80% anti and 20% syn.
Figure 1. B2PLYP-D3/VTZ optimized geometries of the four conformers of MACR-oxide. The relative stabilities (kcal
mol1) are computed from zero-point energy corrected CCSD(T)-F12/CBS(TZ-F12,QZ-F12)//B2PLYP-D3/cc-pVTZ
energies.
The rates and mechanisms for unimolecular decay of the four-carbon unsaturated carbonyl oxide intermediates are
predicted to differ significantly for MACR-oxide and MVK-oxide, and are further expected to be highly dependent on the
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conformational form.8-9, 17, 27-28 Prior theoretical studies indicate that unimolecular decay of various MVK-oxide and MACR-
oxide conformers will proceed by distinctly different pathways under thermal conditions (298 K, high pressure limit). For
MVK-oxide, syn conformers decay slowly (33 s-1) via 1,4 H-atom transfer to yield OH radical products,8, 17, 27-28 while anti
conformers are predicted to undergo rapid unimolecular decay (ca. 2000 s1) via an electrocyclic ring closure mechanism,
forming a 5-membered cyclic peroxide known as dioxole.8, 17, 28 The 1,4 H-atom transfer pathway is not available for MACR-
oxide. For MACR-oxide, anti conformers are expected to decay rather slowly (10 s-1) by ring closure of the carbonyl oxide
group to form a cyclic dioxirane.9, 28 In contrast, the syn-cis conformer of MACR-oxide is predicted to undergo rapid
unimolecular decay (2500 s-1) to form dioxole.9, 28
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For MVK-oxide and MACR-oxide conformers that undergo slow unimolecular decay, bimolecular reactions with water
vapor or other trace species may play a role in their atmospheric chemistry.27-30 The effective bimolecular rate coefficient
(298 K, 100% RH) for anti-MACR-oxide with water monomer and dimer is predicted to be keff = 8.7  10-15 cm3 molecule1
s-1.30 By contrast, the bimolecular reaction of syn-MVK-oxide with water vapor is predicted to be negligibly slow (keff = 2.0
 1018 cm3 molecule-1 s-1).30 The rates and mechanisms for many atmospheric reactions of the four-carbon unsaturated
Criegee intermediates are ripe for further study.
Recently, our team introduced a new synthetic approach to generate MVK-oxide directly. This involved UV photolysis
of a 1,3-diiodobut-2-ene precursor to create a resonance-stabilized mono-iodoalkene radical that reacts with O2 to produce
MVK-oxide.17-18 Here, we demonstrate an analogous reaction scheme to generate MACR-oxide, starting from a 1,3-diiodo-
2-methylprop-1-ene precursor, which demonstrates the generality of this strategy to prepare unsaturated Criegee
intermediates. In both cases, we take advantage of resonance stabilization of the mono-iodoalkene radical in order to
generate the four-carbon unsaturated Criegee intermediates from isoprene ozonolysis.
Thus far, MVK-oxide has been characterized experimentally using IR action spectroscopy,17 UV-vis spectroscopy on its
first strong * electronic transition, and VUV photoionization.18 The IR action spectrum was obtained by excitation of
MVK-oxide with two quanta of CH stretch and detection of the resultant OH products. The UV-vis excitation spectrum was
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recorded via depletion of the associated VUV photoionization signal (m/z=86) as well as detection of the resulting O D
products. Extensive theoretical calculations have also been carried out for the four conformers of MVK-oxide to predict
their IR spectra, electronic transitions, and ionization energies, as well as various unimolecular and photochemical decay
processes. These fundamental experimental and theoretical studies lay the groundwork for future investigations of
unimolecular and bimolecular reactions of MVK-oxide under atmospheric temperature/pressure conditions.
Prototypical Criegee intermediates examined previously have large oscillator strengths (f  0.1) involving *
transitions associated with the four  electrons of the carbonyl oxide (C=O+O) group.22-24, 31-32 The UV spectra are peaked
at 335 nm for CH2OO,22, 33-34 ca. 320 nm for syn-CH3CHOO,23, 35-36 (CH3)2COO and CH3CH2CHOO,24, 37 and ca. 360 nm for
anti-CH3CHOO.35 By contrast, the electronic spectrum associated with the first * transition of MVK-oxide (six 
electrons), arising from overlapping spectra of four conformers, is shifted to longer wavelength and peaks at 388 nm.18 In
general, the UV-vis spectra are relatively broad and unstructured, although CH2OO exhibits some oscillatory structure in
the long wavelength tail region33-34, 38-39 ascribed to vibrational resonances.39-40 Theoretical calculations indicate that the
1* excited electronic state accessed upon UV-vis excitation of the Criegee intermediates couples via conical intersection
to repulsive potential(s), which lead to O 1D and singlet carbonyl products.32, 40-41
Several groups are pursuing other promising approaches for direct detection of Criegee intermediates formed in
ozonolysis reactions. These include infrared detection of Criegee intermediates from -pinene,42 Fourier transform
microwave spectroscopy of CH2OO from ethylene,43 spin traps and proton-transfer reaction mass spectrometry detection of
Criegee intermediates from -pinene,44 and chemical ionization mass spectrometry of CH2OO and cyclohexene-derived
Criegee intermediates.45
In this paper, we present the first direct observation of the MACR-oxide Criegee intermediate. We introduce a new
synthetic method to produce MACR-oxide and we demonstrate 10.5 eV photoionization detection of MACR-oxide on the
parent m/z=86 mass channel. We provide the first experimental study of the electronic spectrum of MACR-oxide by means
of UV-vis induced depletion of the photoionization signal and generation of O 1D products, and complementary high-level
calculation of the absorption spectra for the four conformers of MACR-oxide. The electronic spectrum of MACR-oxide is
compared and contrasted with that for MVK-oxide,18 since both systems have extended conjugation across the vinyl and
carbonyl oxide groups. In addition, we examine the UV-vis induced dissociation dynamics of MACR-oxide to MACR X 1A
+ O 1D products and associated theoretical predictions. We anticipate that UV-vis excitation, when coupled with transient
absorption or cavity ringdown spectrometers,16, 46-47 will enable spectroscopic detection of MACR-oxide in future laboratory
studies of its unimolecular decay dynamics and bimolecular reactions with atmospheric species.
2. Results
2.1 Laboratory synthesis of MACR-oxide
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A novel synthetic route is used to generate the methacrolein oxide (MACR-oxide) Criegee intermediate starting from
the (E)-1,3-diiodo-2-methylprop-1-ene precursor. In devising a synthetic route to the precursor, several attributes were
important. Allylic iodides are very reactive and light-sensitive species,48 and their synthesis and handling must be performed
with significant care. We viewed the synthesis, purification, storage, and use of an allylic diiodide containing the 3,3-
diiodoprop-1-ene motif (CH2=CHCHI2) as fraught with potential problems. Thus, we chose a less reactive 1,3-diiodo-2-
prop-1-ene motif, bearing allylic and sp2-hybridized C–I bonds. Given the sensitivity of the final diiodide, a stable
intermediate near the end of the synthesis that would be easily stored was considered essential.
A reaction scheme showing each step of the precursor synthesis is shown in Scheme 2. The optimized synthesis
commenced with 150 mmol diethyl malonate, which was deprotonated with in situ generated sodium ethoxide (NaOEt) and
methylated with methyl iodide (MeI) to afford the methylated product A in 97% isolated yield.49 Diethyl methylmalonate
(A) was deprotonated with sodium hydride (NaH) and alkylated with CHI3 to generate diiodide B in 80% after workup.50
Intermediate B, used without purification, was subjected to a tandem hydrolysis/elimination mediated by KOH in refluxing
ethanol/water (EtOH/H2O 3:1). The carboxylic acid C was isolated after acidic workup and column chromatography in 55%
yield as a single double bond isomer. The solid acid C proved to be an excellent intermediate to store material.
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Scheme 2. Synthetic route to generate (E)-1,3-diiodo-2-methylprop-1-ene (F).
Reduction of the acid C was performed with lithium aluminum hydride at room temperature to afford alcohol D in 52%
yield after purification. Alcohol D was treated with methanesulfonyl chloride, triethylamine, and catalytic DMAP (4-N,N-
dimethylaminopyridine) to generate mesylate E in 82% yield.51 The reactive mesylate was directly subject to NaI in acetone
to perform the final substitution. The reaction was conducted in a dark fume hood with the reaction vial covered by
aluminum foil to exclude light. The desired precursor (E)-1,3-diiodo-2-methylprop-1-ene (F) was obtained in 85% yield
after purification by column chromatography. The precursor F could be stored in the dark in a refrigerator for 2–3 weeks.
The Supporting Information (SI) provides full details on the multistep synthesis of the precursor (Sec. S1), along with its
analytical characterization (Figures S1-S3) and related theoretical calculations (Figure S4, Table S1).
A novel synthetic route is then used to generate the methacrolein oxide (MACR-oxide) Criegee intermediate starting
from the (E)-1,3-diiodo-2-methylprop-1-ene precursor. The 1,3-diiodo-2-methylprop-1-ene precursor absorbs strongly at
248 nm (Figure S2) and is expected to preferentially dissociate the weaker allylic C(1)-I bond to form a resonance stabilized
mono-iodo allylic radical intermediate, Int (1), as shown in Scheme 3.
O
O
O
O
O
3
1
2
O
O2
h
-I
syn, cis
syn, trans
I
I
I
I
-I
I
O
O
4
O
O
anti, cis
anti, trans
(E)-1,3-diiodo-2-
methylprop-1-ene
Int (1)
Int (2)
MACR-oxide
Scheme 3. Synthetic route to generate MACR-oxide.
Resonance delocalization will lead to radical character on the C(3) carbon. Subsequent reaction with O2 at C(3) will transiently
form an iodoalkene peroxy radical, Int (2), prior to dissociation of I and formation of MACR-oxide. (Alternatively, if O2
adds at the C(1) carbon site of Int (1), then dioxole would likely be formed, as shown in Scheme S2 of Ref. 17, instead of
MACR-oxide.) The internally excited Int (2) should permit internal rotation about its single C-C and C-O bonds, and thus
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we assume that all four conformers of MACR-oxide are formed. An analogous reaction scheme was recently utilized to
generate MVK-oxide.17-18
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The minimum energy structures and zero-point energy (ZPE) corrected energies computed for the four conformers of
MACR-oxide are given in Figure 1 and Table 1, and are in good agreement with a previous theoretical prediction.9 See SI
Sec. S2 for related theoretical calculations (Figure S5, Tables S2-S4). The four conformers have similar energies, differing
by less than 3.2 kcal mol-1, with the anti-trans conformer predicted to be most stable. The computed barriers for
interconversion between syn and anti conformers are quite high (ca. 20 kcal mol1), while those between cis and trans
conformers are relatively low (ca. 9 kcal mol-1).9
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Table 1. Ground state stability (minima) and vertical (VIE) and adiabatic (AIE) ionization energies computed at the
CCSD(T)-F12/CBS(TZ-F12,QZ-F12)//B2PLYP-D3/cc-pVTZ level of theorya for the four conformers of MACR-oxide.
MACR-oxide
Conformer
Minimaa /
kcal mol-1
VIEc,d / eV
AIEb,d / eV
anti-cis
anti-trans
syn-cis
3.18
0.00
0.91
2.50
8.90
8.85
9.17
8.90
8.77
8.73
9.01
8.78
syn-trans
aMinima derived from other theoretical methods and previous work are given in Table S3. bIncluding ZPE correction. cWithout
ZPE correction. dIncludes an approximate higher level excitation and core-valence correction of 0.07 eV obtained from
CCSDT(Q)/cc-pVDZ and CCSD(T)/CBS(cc-pcVTZ,cc-pcVQZ) calculations for CH2CHCHOO.
2.2. Electronic transitions of MACR-oxide: Theoretical predictions and experimental findings
The present study focuses on characterizing MACR-oxide through the strong * electronic transitions anticipated
for the four conformers based on CASSCF/CASPT2 calculations (detailed in SI Sec. S2). The theoretical calculations
indicate that two distinct excited singlet states of * character will have high oscillator strength (f  0.1, Table 2) and are
therefore expected to be ‘optically bright’. Vertical transitions to the 11* state of the four conformers of MACR-oxide
are predicted between 342 and 380 nm (3.62 to 3.26 eV), while the second singlet *← transitions are predicted between
228 and 304 nm (5.43 to 4.07 eV). The predominant orbitals contributing to the *← transitions are shown in Figure 2.
The orbitals show that excitation to the 11* state is mainly associated with electronic promotion from the HOMO ()
orbital to the LUMO (*) orbital, the latter of which shows increased antibonding character around the carbonyl oxide
moiety. In contrast, 21* excitation to the LUMO+2 (*) orbital is associated with additional antibonding character in
the vinyl substituent.
Table 2. Verticalꢀexcitation energies (VEE/eV) ꢀcorresponding wavelengths (/nm), andꢀoscillator strengths (f)ꢀ computed
at CASPT2(12,10)/AVDZ level of theory forꢀ * electronic transitions with high oscillator strengths for the four
conformers of MACR-oxide.a
MACR-oxide
Conformer
VEE / eV
(  nm)
fꢀ
anti-cis
anti-trans
syn-cis
3.26 (380)
4.07 (304)
3.31 (374)
4.31 (288)
3.62 (342)
4.36 (285)
3.29 (377)
5.43 (228)
0.093
0.083
0.116
0.082
0.057
0.062
0.094
0.110
syn-trans
aCompilation of vertical excitation energies and oscillator strengths computed for the lowest six singlet electronic transitions of
each conformer are given in Table S5.
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Figure 2. Selected orbitals within the active space of the CASSCF/CASPT2 calculations used to compute the lowest six
singlet vertical transitions for the four conformers of MACR-oxide. (All orbitals are shown in Figure S6.) The orbitals
displayed are of  and * nature and are involved in the electronic transitions associated with the highest oscillator strength
(Table 2). The arrows illustrate orbital promotions involved in forming the designated excited singlet states of MACR-
oxide.
Experimentally, the diiodo alkene precursor is entrained in a 20% O2/Ar gas mixture, pulsed into a quartz capillary
reactor tube, and photolyzed at 248 nm with an excimer laser (see SI Sec. S3). MACR-oxide is collisionally stabilized and
cooled in a supersonic expansion as it passes into a collision free region for spectroscopic studies. MACR-oxide is
initially detected by photoionization using 10.5 eV (118 nm) VUV radiation, generated by frequency tripling the 3rd
harmonic output of a Nd:YAG laser, on the m/z=86 parent mass channel of a time-of-flight mass spectrometer (Figure
S7). The 10.5 eV photoionization energy exceeds the ionization thresholds computed for the four MACR-oxide
conformers (8.7-9.0 eV, Table 1). Other isomers that could potentially be generated in the source and ionized at 10.5 eV
are discussed later.
Resonant excitation on the first * transition of MACR-oxide is observed as a UV-vis induced depletion of the
ground state population of one or more of the conformers. The resultant ground state depletion is detected after a short
time delay (t  50 ns) as a reduced VUV photoionization signal at m/z=86. Figure 3 shows a representative ground state
depletion in which resonant UV excitation induces a significant decrease in the VUV photoionization signal at m/z=86.
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Figure 3. Mass spectra (m/z=86) arising from photoionization of MACR-oxide using 118 nm (10.5 eV) VUV radiation.
The top trace (blue) shows the photoionization signal. The middle trace (dark blue) shows a significant reduction in the
photoionization signal that occurs upon resonant UV excitation, which results in ground state depletion. The lower trace
(violet) shows the depletion signal (UV on – UV off). The right panel shows a schematic energy level diagram illustrating
the    electronic transition and ionization limit (shaded) for the MACR-oxide Criegee intermediate.
The magnitude of the depletion, expressed as (N0 – N)/N0 with ground state abundances N0 before and N after UV
excitation, increases with UV power to a maximum depletion of ca. 35% (Figure S8). A minimum depletion of 2-3% can
be reliably measured. The corresponding absorbance, ln (N/N0), scales linearly with UV power up to ca. 3.6 mJ/pulse,
demonstrating a one-photon process. The significant ground state depletion indicates a strong electronic transition, as
observed previously for other Criegee intermediates.18, 22-24
A qualitative estimate of the absorption cross section () of MACR-oxide is evaluated by dividing the absorbance by
the photon flux  (mJ/cm2) of the focused UV-vis beam in the interaction region. At an UV power of 2.5 mJ/pulse and an
approximate area of 0.05 cm2, corresponding to a photon flux of 50 mJ/cm2, we estimate the absorption cross section for
MACR-oxide at 380 nm to be ~3  10-18 cm2 molecule-1 and a corresponding atmospheric lifetime of 10 s. This estimate
does not consider that the four MACR-oxide conformers may have different ground state populations, photoionization
efficiencies at 10.5 eV, and/or absorption cross sections. The estimated  will be a lower limit if other possible isomers
contribute to the photoionization signal at 10.5 eV.
The electronic spectrum associated with excitation to the 11* state of MACR-oxide is obtained by scanning a
broadly tunable BBO optical parametric oscillator (OPO, see SI Sec. S3) across the UV-vis region from 315 to 500 nm,
while monitoring the induced depletion of the VUV photoionization signal at m/z=86. The resultant UV-vis spectrum,
recorded with 1 and 0.5 nm step sizes in the 315-380 and 380-500 nm regions, respectively, is shown in Figure 4.
The spectrum is normalized to laser power, which is maintained near 2.5 mJ/pulse to ensure linear scaling with power.
The data points are averages of repeated measurements with 1 uncertainty indicated by the shaded region. A smoothed
version of the spectrum is superimposed on the plot to guide the eye. The resultant experimental spectrum for MACR-
oxide is broad, spanning across the entire 315 to 500 nm spectral region, and peaks at 380 nm. The peak of the
experimental spectrum is in excellent accord with the computed vertical transitions (Table 2) to the 11* state of the four
MVK-oxide conformers as shown in Figure 4. On the shorter wavelength side, the experimental spectrum initially falls
off, exhibiting a dip at 343 nm to ca. 70% of its maximum absorbance, and then increases again, the latter likely due to the
onset of excitation to the higher energy 21* state that will be explored in future work. On the longer wavelength side,
the spectrum falls off to half maximum at ca. 436 nm and drops to a minimum observable level at ca. 490 nm. Weak
oscillatory structure is evident in the longer wavelength side of the spectrum with local maxima at 416.4, 430.9, and 448.1
nm, as determined from fits of the local structure with Lorentzian profiles (see SI Sec. S4, Table S6, Figure S9), and will
be discussed later. Only CH2OO, the simplest Criegee intermediate, has shown analogous oscillatory structure on the long
wavelength side of its broad UV absorption band.33-34, 38-39
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Figure 4. Experimental UV-vis spectrum of MACR-oxide from 315 to 500 nm derived from depletion of the
photoionization signal on the m/z=86 mass channel. The corresponding absorbance (points) is normalized to the UV-vis
laser power. The solid line represents a smoothed curve (11 point smooth) through the experimental data and the shaded
area illustrates the experimental uncertainty derived from repeated measurements. For comparison, CASPT2(12,10)/AVDZ
vertical excitation energies and associated oscillator strengths (bars) are shown for promotion of MACR-oxide to the excited
11* state for the anti-cis (blue), anti-trans (green), syn-cis (red) and syn-trans (violet) conformers. Also shown is the
overall MACR-oxide electronic spectrum (dashed line) predicted for the four conformers.
For comparison, the purely electronic excitation spectrum originating from the ground state of each conformer of
MACR-oxide was theoretically computed using an approach similar to that implemented in Newton-X.52-56 For each
conformer, vertical transitions were computed for an ensemble of 300 initial ground state geometries sampled using a
Wigner distribution based on normal mode harmonic frequencies. The transitions were broadened (0.25 eV Lorentzian
lineshape) and summed to generate the absorption spectra shown in Figure 5 (see SI Sec. S5, Figure S10). The computed
spectra for the four conformers are overlapping with largest contributions to the first * transition in the 370-440 nm
region for anti-trans, anti-cis, and syn-trans conformers and in the 355-380 nm region for the syn-cis conformer.
Contributions from the second * transition for each conformer are predicted at shorter wavelength and are again
overlapping, and merge to some extent with those from the first transition.
The cumulative absorption spectrum for MACR-oxide (rescaled by a factor of 1.5 in Figure 5) is obtained by summing
the absorption spectra for each conformer and assuming equal population of the conformers. The resultant cumulative
spectrum for MACR-oxide peaks at 383 nm and falls off on the longer wavelength side to half maximum at 475 nm. On
the shorter wavelength side, the cumulative spectrum drops by ca. 15% at 345 nm and continues with similar absorbance
in a relatively flat region arising from overlapping contributions of the two ← transitions down to ca. 275 nm before
falling off to half maximum at ca. 230 nm. The theoretically predicted spectrum for the * transitions of the four
conformers of MACR-oxide agrees well with the 380 nm peak and broad span of the experimental spectrum. We discuss
the origin of the oscillatory structure below.
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Figure 5. CASPT2(12,10)/AVDZ vertical excitation energies (vertical bars) to the 11* and 21* states and associated
oscillator strengths for anti-cis (blue), anti-trans (green), syn-cis (red) and syn-trans (violet) conformers of MACR-oxide.
The calculated electronic absorption spectra (solid curves) are derived for a harmonic-oscillator Wigner distribution of
ground state configurations for each of the four conformers of MACR-oxide. The cumulative MACR-oxide electronic
spectrum (dashed black curve) is the sum of the four individual spectra, assuming equal ground state populations, but reduced
in scale by a factor of 1.5.
2.3. Photodissociation dynamics of MACR-oxide
UV-vis excitation of MACR-oxide results in prompt dissociation and yields O 1D products that are readily detected by
2+1 resonance-enhanced multiphoton ionization (REMPI), as found previously for other Criegee intermediates.18, 39, 57-59
Here, we examine the UV-vis induced dissociation dynamics of MACR-oxide conformers to MACR X 1A + O 1D
products from experimental and theoretical perspectives. Starting with theory, we map out potential energy curves
(unrelaxed) along the lowest, spin-allowed O-O dissociation coordinate for the most stable anti-trans conformer of
MACR-oxide. The resultant diabatic potential curves (unrelaxed) are shown in Figure 6.
Figure 6. CASPT2(12,10)/AVDZ potential energy curves (unrelaxed) calculated along the O-O bond stretching coordinate
for the lowest seven singlet states of the most stable conformer of MACR-oxide (anti-trans). Vertical excitation from the
ground S0 electronic state (black) to the 11* state (green) is predicted at 3.31 eV (374 nm). The 11* state is crossed by
(n/* dissociative states (gray) at extended O-O bond distances. Predissociation of the 11* state via (n/* states
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1
leads to the lowest spin-allowed dissociation asymptote of trans-MACR X A + O D products at 2.46 eV. The higher
asymptotic channel results in trans-MACR a 3A + O 3P products at 3.26 eV. (Right panel) Computed vertical electronic
transition (bar) and associated absorption spectrum (curve) for the * transitions based on a harmonic-oscillator Wigner
distribution of initial configurations in the S0 state.
Vertical excitation of the anti-trans conformer from the ground S0 electronic state to the 11* excited state (3.31 eV)
is predicted to access a repulsive region of the excited state potential. The vertical electronic transition and broad
simulated absorption spectrum for anti-trans-MACR-oxide are also shown in Figure 6. The 11* excited state couples
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via conical intersection (estimated at 2.83 eV) with a repulsive potential(s) at extended O-O bond distances and leads to
the lowest spin-allowed dissociation asymptote of trans-MACR X 1A + Oꢀ1D. The zero-point corrected energy required
for spin-allowed dissociation of the anti-trans conformer of MACR-oxide to trans-MACR X 1A + O 1D is computed to be
2.08 eV utilizing a relaxed optimization at large O-O separation (see SI Sec. S5 and Tables S7-S8). ZPE dissociation
energies for other MACR-oxide conformers (Table S8) are evaluated by taking into account their relative ground state
stabilities (Table 1) and the computed energy splitting between the cis and trans conformers of the MACR product.
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Experimentally, velocity map imaging (VMI) experiments are carried out with UV-vis excitation of MACR-oxide and
detection of O 1D fragments arising from the lowest spin-allowed product channel. Details regarding VMI experimental
conditions are discussed in the SI (Sec. S3). The velocity and angular distributions of the O 1D products reveal
information on the energy partitioning to products and the timescale for dissociation, respectively. VMI images of the O
1D products are recorded (after background subtraction) at discrete excitation wavelengths from 385 to 471 nm,
specifically near the peak of the UV-vis spectrum (385 nm, Figure 7), the peaks of the weak oscillatory structure (416,
431, and 448 nm), and close to the extreme of the long wavelength tail region (471 nm, Figure 7). The O 1D signal drops
off rapidly at longer excitation wavelengths with only a very weak signal at ca. 500 nm (insufficient for an image), which
is consistent with the depletion spectrum (Figure 4). The theoretical calculations confirm that dissociation of MACR-
oxide to MACR X 1A + O 1D products should be energetically accessible throughout the observed spectral region (Table
S8, dissociation energies of 1.97-2.18 eV, corresponding to 629-568 nm, depending on the conformer).
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Figure 7. Total kinetic energy release (TKER) distributions (with black curve through data points from polynomial fit) to
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the MACR + O D products resulting from UV-vis excitation of MACR-oxide at 385 nm (violet, top panel) and 471 nm
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(blue, lower panel). The TKER distributions are deduced from analysis of the O D velocity map images (insets). The
double-sided vertical arrows represent the polarization of the UV-vis OPO (parallel to the detector plane).
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The O D VMI images at 385 and 471 nm (Figure 7) exhibit anisotropic angular distributions indicative of rapid
dissociation compared to the rotational period of MACR-oxide (ca. 100 ps). This demonstrates that electronic excitation of
MACR-oxide to the 11* state at   500 nm accesses regions of strong coupling to repulsive potential(s) (Figure 6) that
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result in rapid dissociation to MACR X A + O D products. Similarly, the anisotropic VMI images of O D products
recorded at the local maxima of the weak oscillatory structure (416, 431, and 448 nm) show that the excited state accessed
is short-lived.
The rapid dissociation ( 100 ps) of MACR-oxide upon electronic excitation to the 11* state precludes its
subsequent detection by photoionization on the parent m/z=86 mass channel after a 50 ns experimental time delay. As a
result, the UV-vis spectrum of MACR-oxide on the first * transition obtained by the depletion method will be
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equivalent to a standard absorption method. Although not the main focus of the present study, prompt dissociation to O 1D
products is also seen for MACR-oxide promoted to the 21* state at 205 nm (SI Sec. S6, Figure S11).
Excitation of MACR-oxide in the 385 to 471 nm range gives rise to MACR X 1A + O 1D products with broad and
unstructured total kinetic energy release (TKER) distributions having remarkably similar average translational energies
(ca. 2700 cm1) and breadths (FWHM  3000 cm-1) as shown in Figure 7 (Table S9). The similarity of the TKER
distributions is notable given that the range of excitation wavelengths results in a nearly 5000 cm-1 change in energy
available to products (e.g. decrease from ca. 10,200 to 5500 cm-1 for anti-trans conformer). This suggests the possibility
of a barrier, e.g. associated with the conical intersection (roughly estimated at 2.83 eV for the anti-trans conformer), along
the reaction path to products. The energy associated with the barrier is expected to flow preferentially into translational
energy, while excess energy above the barrier would be statistically distributed and principally result in vibrational
excitation of MACR.60 The dissociation energy predicted for anti-trans MACR-oxide to trans-MACR X 1A + O 1D
products is 2.08 eV (Table S8), which suggests that a barrier energy of 0.75 eV (6000 cm-1) would flow into translation.
This is in good accord with the range of kinetic energies observed in the experimental TKER distributions. Finally, we
note that excitation at energies in the vicinity of the barrier associated with the conical intersection, yet above the MACR
X 1A + O 1D asymptote, may access quasi-bound vibrational levels in the excited 11* state of MACR-oxide. This, in
turn, could give rise to the weak oscillatory structure observed in the electronic spectrum at long wavelengths, although
higher-level calculations of the conical intersection region(s) will be needed to test this hypothesis.
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3. Discussion
3.1 Weak oscillatory structure at long wavelengths
Here, we examine the origin of the weak oscillatory structure observed in the long wavelength tail region of the
experimental spectrum of MACR-oxide (Figure 4). The oscillatory structure is superimposed on a broad profile spanning
from 371 to 500 nm, which is simulated as a Lorentzian profile with peak at 374.8 nm and accounts for ca. 90% of the
total signal. The local structure associated with the weak oscillations, together accounting for about 10% of the total
signal, is fit using three Lorentzian profiles with local maxima at 416.4, 430.9, and 448.1 nm (SI Sec. S4). The local
maxima are separated by ca. 810 and 890 cm-1, respectively. The simulation of the weak oscillations yields relatively
large and variable breadths (FWHM) of 1810, 310, and 560 cm-1, respectively.
The weak oscillatory structure observed for MACR-oxide is reminiscent of the more extensive progression seen
previously in the long wavelength tail region of the electronic spectrum of the simplest Criegee intermediate CH2OO.33-34,
38-39
In CH2OO, the progression was attributed to short-lived resonances originating from congested vibrational structure
involving several modes (e.g. O-O stretch and COO bend)38 in the excited B 1A electronic state.39-40 The emergence of
oscillatory structure in the long wavelength region of the MACR-oxide spectrum is surprising, because the theoretical
calculations indicate that multiple conformers will have overlapping electronic spectra in this region. (The current
theoretical approach yields purely electronic transitions and cannot predict vibrational structure.)
The average spacing of the oscillatory structure evident in the MACR-oxide electronic spectrum (ca. 850 cm-1) is
larger than that observed in the long wavelength tail region of CH2OO, where an average spacing of ca. 610 cm-1 was
dominant in an extended progression. For comparison, the vibrational frequency of the O-O stretch (harmonic) is
predicted to be ca. 900 cm-1 for CH2OO in the excited 11* state,38 which is in accord with typical O-O stretches in the
excited states of peroxide molecules.61-65 The oscillatory structure in the MACR-oxide spectrum likely has contributions
from several vibrational modes including the O-O stretch (dissociation coordinate) and/or multiple conformers. This
could explain the greater breadth and variability of the oscillatory features in the MACR-oxide spectrum compared to the
average breadth (ca. 300 cm-1) and deviation seen in the CH2OO UV spectrum.33-34, 38-39
Finally, VMI images recorded at the local maxima in the MACR-oxide spectrum reveal rapid dissociation to MACR
X 1A + O 1D products, as has been found previously for CH2OO.39 Thus, by analogy to CH2OO, the broad oscillatory
structure in the long wavelength region of the MACR-oxide spectrum is ascribed to short-lived vibrational resonances
associated with the excited 11* electronic state, which decay by nonadiabatic coupling to repulsive singlet states.
3.2 Comparison of MACR-oxide and MVK-oxide
Experimentally, the peak of the UV-vis spectrum of MACR-oxide (380 nm) is similar to that reported recently for
MVK-oxide (388 nm), the other four-carbon, unsaturated Criegee intermediate from isoprene ozonolysis. However, the
MACR-oxide spectrum falls off more slowly to longer wavelength than MVK-oxide (Figure S12). In addition, the
MACR-oxide spectrum exhibits weak oscillatory structure in the long wavelength tail region, which was not observed for
MVK-oxide. Theory predicts that both MACR-oxide and MVK-oxide have strong electronic transitions to the 11* state
originating from four conformers with broad overlapping contributions to their cumulative spectra. The largest oscillator
strength for MACR-oxide, which is associated with vertical electronic excitation of the most stable anti-trans conformer
(Table 2), is predicted to be about a factor of two weaker than that for the strongest transition for MVK-oxide (anti-trans
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conformer). Similarly, the peak experimental absorption cross section estimated for MACR-oxide is somewhat less than
that estimated for MVK-oxide. This is evident by the higher UV-vis OPO power required to reach the maximum
depletion for MACR-oxide (ca. 3.5 mJ/pulse) than that needed for MVK-oxide (ca. 1 mJ/pulse).
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Additional direct theoretical comparisons can be made between MACR-oxide and MVK-oxide because they are
isomers. This permits direct comparison of the ground state stabilities (using the same method/basis with ZPE correction)
of MACR-oxide and MVK-oxide for the four conformers of each isomer, along with the stabilities of the MACR and
MVK isomer products. Specifically, this comparison shows that the most stable (anti-trans) conformer of MACR-oxide is
5.95 kcal mol1 less stable in absolute energy than the most stable conformer of MVK-oxide (syn-trans).
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In addition, the dissociation energies computed for the MACR-oxide conformers can be directly compared with those
for MVK-oxide (Figure S13). This shows that less energy is required for dissociation of the anti-trans, syn-trans, and
anti-cis conformers of MACR-oxide to the MACR + O 1D product channel than the energy required for all four
conformers of MVK-oxide to the analogous MVK + O 1D product channels. Only the syn-cis conformer of MACR-oxide
requires a similar energy for dissociation as MVK-oxide.
3.3 Electronic transitions of other possible isomers
For MACR-oxide, a maximum UV-vis induced depletion of 35% is observed when detected by 10.5 eV
photoionization on the m/z=86 mass channel. This suggests that more than one isomer (or possibly a dissociative
ionization fragment) may contribute to the photoionization signal at m/z=86. Such additional species do not appear to
strongly absorb UV-vis radiation. To test this hypothesis, we calculate vertical excitation energies and oscillator strengths
(Tables S10-S11) of plausible isomers (e.g. dioxole, dioxirane, methacrylic acid, -dicarbonyl, epoxide), which may result
from unimolecular decay of MACR-oxide as elaborated below.9, 66-67 Atmospheric chemistry of isoprene also generates
isoprene-derived peroxy radicals [HO-C5H8(Iso)-O2] that have an overlapping absorption band in the near UV from 300 to
400 nm.68
The lowest energy pathways for unimolecular decay of MACR-oxide are predicted to be distinctly different for the
four conformers. For the syn-cis conformer, unimolecular decay is expected to start with very rapid 1,5 electrocyclic ring
closure (2500 s-1)28 to form the 5-membered ring of dioxole (4-methyl-3H-1,2-dioxole, Scheme 4)9 that can lead to several
products as outlined below.9, 17, 28
epoxide
O
O
O
O
O
closure
O
O
O
ring
1,2
O
O
O
H
shift
dioxole
syn-cis
O
-dicarbonyl
Scheme 4. Mechanism for syn-cis-MACR-oxide unimolecular decay to dioxole intermediate and subsequent products.
For anti-conformers of MACR-oxide, the lowest energy pathway is predicted to be rather slow decay (10 s-1) via 1,3
ring closure of the carbonyl oxide group to form a three-membered cyclic dioxirane ([3-(prop-1-en-2-yl) dioxirane],
Scheme 5),9 and subsequent products. A small portion of the anti-conformers are predicted to form hot methacrylic acid
(2-methyl-2-propenoic acid, not shown).5 By contrast, the 1,4 H-atom transfer mechanism available to syn-conformers of
MVK-oxide and methyl (or alkyl) substituted Criegee intermediates is not feasible for MACR-oxide because it lacks an -
H in a methyl (or alkyl) group adjacent to the terminal O atom.
O
O
O O
Products
anti-trans
dioxirane
Scheme 5. Mechanism for anti-trans-MACR-oxide unimolecular decay to dioxirane intermediate and subsequent products.
If dioxole and/or dioxirane products are formed and stabilized, e.g. in the reactor tube, they could be ionized at 10.5 eV
(Table S12). However, neither are predicted to have strong electronic transition in the 350 to 500 nm region observed for
MACR-oxide. The first strong electronic transitions of dioxole and dioxirane are predicted to have vertical excitation
energies below 250 nm (Table S10). As shown in Scheme 4, initially formed dioxole will be internally excited and could
decay by O-O bond fission to form a diradical, which could then rearrange by a 1,2 H-atom shift to form a -dicarbonyl
(2-methyl-3-oxoproponal) and/or by ring closure to epoxide (1,2-epoxy-2-methyl-3-propanal) products, and/or undergo
fission to various bimolecular products.9 While such -dicarbonyl and epoxide products could be ionized at 10.5 eV
(Table S12), their first strong electronic transitions are predicted below 200 nm (Table S10). Similarly, methacrylic acid,
if formed, will be ionized at 10.5 eV,69 but the onset of its UV spectrum occurs below 230 nm70 and its strong electronic
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transitions are predicted below 200 nm (Table S10). Finally, dioxiranes with allylic functionality can undergo ring
opening to a dioxy biradical, which can further rearrange or decompose.5, 9, 66-67
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4. Conclusions
MACR-oxide, a four-carbon unsaturated Criegee intermediate generated in isoprene ozonolysis, is synthesized in the
laboratory setting for the first time by photolysis of an (E)-1,3-diiodo-2-methylprop-1-ene precursor and reaction of the
resultant resonance stabilized mono-iodo allylic radical with O2. The electronic spectrum of jet-cooled MACR-oxide is
recorded by a depletion method, in which UV-vis excitation induces depletion of the ground state population of one or
more of its four conformers and results in an associated decrease in the VUV (10.5 eV) photoionization signal on the
m/z=86 parent mass channel. The resultant UV-vis spectrum peaks at 380 nm, spans across the 315-500 nm region, and
exhibits weak oscillatory structure in the long wavelength region. The spectrum increases again below 343 nm, likely due
to the onset of the second * transition. Additional velocity map imaging experiments demonstrate that electronic
excitation of MACR-oxide throughout the entire spectral region results in rapid dissociation (≤ 100 ps) to O 1D products
that are detected by 2+1 REMPI. The rapid dissociation of MACR-oxide in the excited 11* state assures that the
electronic spectrum obtained by the depletion method is equivalent to a direct absorption method. The weak oscillatory
structure of the MACR-oxide spectrum, which is analogous to an extended progression observed previously for CH2OO,33-
34, 39 is likely due to short lived vibrational resonances in the excited 11* state.
Complementary theoretical calculations examined the ground state stabilities of the four MACR-oxide conformers
(within 3.2 kcal mol-1), along with their vertical transitions energies and oscillator strengths. Strong vertical transitions are
predicted to the 11* state in the 3.26-3.62 eV (342-380 nm) region and to the 21*state in the 4.07-5.43 eV (228-304
nm) region. These transitions are nominally associated with the carbonyl oxide and vinyl groups, respectively. UV-vis
absorption profiles for the MACR-oxide conformers are also computed using a Wigner distribution of initial
configurations. The resultant cumulative absorption spectrum for the first * transition, assuming equal contributions
of the four conformers, is computed to peak at 383 nm and agrees well with the experimental spectrum.
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MACR-oxide and its isomer MVK-oxide, the other four-carbon unsaturated Criegee intermediate formed in isoprene
ozonolysis, exhibit similar strong absorption spectra, peaked at 380 nm and 388 nm, respectively, arising from the first
* transitions of their four conformers. The MACR-oxide spectrum extends to longer wavelength than MVK-oxide,
and also displays weak oscillatory structure not seen for MVK-oxide. The electronic spectra of MACR-oxide and MVK-
oxide, both with extended conjugation across the carbonyl oxide and vinyl groups, are shifted to longer wavelength than
previously investigated Criegee intermediates, e.g. CH2OO, CH3CHOO, and (CH3)2COO. Direct theoretical comparison of
four-carbon isomers shows that the lowest energy conformer (anti-trans) of MACR-oxide is less stable (by ca. 6.0 kcal
mol1) than the lowest energy conformer (syn-trans) of MVK-oxide. In addition, less energy is required for dissociation of
the lowest energy conformer of MACR-oxide to MACR X 1A + O 1D (48.0 kcal mol1) than that for MVK-oxide to MVK
X 1A + O 1D (52.0 kcal mol-1). Finally, MACR-oxide and MVK-oxide are predicted to have very different unimolecular
decay pathways and bimolecular reactivity with water vapor and potentially other atmospheric species.28-30
The first identification of the four-carbon unsaturated MACR-oxide Criegee intermediate presented in this work is based
1
on laboratory synthesis, VUV photoionization, UV-vis spectroscopy, and photo-induced dissociation to MACR X A +
O 1D products. These advances are expected to enable future studies of its conformer-dependent unimolecular decay
processes and bimolecular reactions with key atmospheric species.
ASSOCIATED CONTENT
Additional material on the synthesis of the (E)-1,3-diiodo-2-methylprop-1-ene precursor, details of electronic structure
calculations, spectroscopic methods and analysis, including Figures S1-S13 and Tables S1-S12.
AUTHOR INFORMATION
Corresponding Authors
*milester@sas.upenn.edu
*pwalsh@sas.upenn.edu
Notes
Present address: Department of Chemistry, University of Louisiana at Lafayette, Lafayette, LA 70503
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported by the U.S. Department of Energy - Basic Energy Sciences under grant DE-FG02-87ER13792
(MIL). Partial support was provided through the National Science Foundation under grants CHE-1664572 (MIL) and CHE-
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1464744 (PJW). BM acknowledges a postdoctoral fellowship from the European Union’s Horizon 2020 research and
innovation programme under the Marie Skłodowska-Curie Grant Agreement PhARRAO - 746593. The authors thank T. N.
V. Karsili (University of Louisiana) for help on the theoretical spectral simulations and Amy Green (University of
Pennsylvania) for carrying out preliminary measurements. NT thanks the Thai government for financial support. This
material is based in part on research at Argonne National Laboratory supported by the U.S. Department of Energy, Office
of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under Contract
No. DE-AC02-06CH11357.
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Optimized geometries of the four conformers of MACR-oxide.
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Selected orbitals of π and π* character computed for the strong electronic transitions of the four conformers
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Mass spectra arising from photoionization of MACR-oxide with and without UV excitation at 385 nm.
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Experimental UV-vis spectrum of MACR-oxide from 315 to 500 nm derived from depletion of the
photoionization signal.
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Calculated vertical excitation energies and electronic absorption spectra for the four conformers of MACR-
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Potential energy curves calculated along the O-O bond stretching coordinate leading to MACR + O
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Velocity map images and total kinetic energy release for MACR + O D products following UV-vis excitation
of MACR-oxide.
106x141mm (150 x 150 DPI)
ACS Paragon Plus Environment

Page 25 of 25
Journal of the American Chemical Society
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Table of Contents figure
44x41mm (300 x 300 DPI)
ACS Paragon Plus Environment