Computational and Theoretical Chemistry 1102 (2017) 114–126

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Computational and Theoretical Chemistry

journal homepage: www.elsevier.com/locate/comptc

Theoretical Study on the Gas Phase Reaction of Allyl Bromide with

Hydroxyl Radical
Yunju Zhang a,⇑, Yuxi Sun a, Jingyu Sun b, Rongshun Wang c
a
Key Laboratory of Photoinduced Functional Materials, Mianyang Normal University, Mianyang 621000, PR China
b
Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical
Engineering, Hubei Normal University, Cihu Road 11, Huangshi, Hubei 435002, PR China
c
Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Renmin Road 5268, Changchun, Jilin 130024, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Mechanisms and reaction channels of the allyl bromide (CH2@CHCH2Br) with OH reaction are studied
Received 13 November 2016 using quantum chemistry. It is predicted that the H(or Br)-abstraction and addition/elimination mecha-
Received in revised form 31 December 2016 nisms have been revealed on potential energy surface (PES). Direct H-abstract from the ACH2Br group of
Accepted 5 January 2017
CH2@CHCH2Br leading to h-P1 (CH2CHCHBr + H2O) is dominant. As for addition/elimination mechanism,
Available online 6 January 2017
it is shown that the reaction is initiated by the addition of OH radical to the C@C bond of CH2@CHCH2Br to
barrierlessly generate the intermediates IM1 and IM2, respectively. Multichannel RRKM theory and vari-
Keywords:
ational transition-state theory (VTST) are employed to evaluate the rate constants of temperature- and
OH
Allyl bromide
pressure-dependent. The calculated rate constants are in good agreement with the available experimen-
Reaction mechanism tal data. At 100 Torr with helium as bath gas, IM3 (CH2OHCHBrCH2) formed by collisional stabilization
Rate constants and the final products P1 (CH2OH + CH2CHBr) are the major product in the temperature range of 200–
Photolysis 700 K and 700–1000 K, respectively. The production of CH2@CHCHBr via hydrogen abstraction becomes
dominant at high temperatures (T P 1000 K). Time-dependent DFT (TD-DFT) calculations indicate that
IM1-IM4, IM6, IM8 and IM9 take photolysis easily in the sunlight at the wavelength of 333 nm,
244 nm, 327 nm, 313 nm, 298 nm, 305 nm and 428 nm, once they are generated.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
Halogenated organic contaminants (HOCs) mainly include the
fluorinated organic compounds (FOCs), chlorinated organic com-
pounds (COCs) and brominated organic compounds (BOCs), which
show the characteristics of persistent organic pollutants in envi-
ronment. Chlorinated organic compounds and brominated organic
compounds contain either chlorine or bromine atoms, and thus
have ozone depletion potential (ODP) [1]. Because bromine atoms
and brominated organic compounds are estimated to be 40–50
times more effective than chlorine atoms and chlorinated organic
compounds in ozone destruction, brominated organic compounds
are particularly problematic in processes related to climate
changes and play a significant role in the depletion of the strato-
spheric ozone [2]. Allyl bromide is widely used in industrial and
agricultural production as raw materials, solvents and so on, and
it can be released into environment through a variety of wastewa-
ter streams. In addition to their environmental effects, a number of
studies have reported that health effects have also been identified.
⇑ Corresponding author.
For example, allyl bromide could irritate eyes, skin and respiratory
system.
Experimentally, the reactions involving allyl bromide (CH2-
@CHCH2Br) with many radicals and molecules have been investi-
gated extensively, including reactions such as CH2@CHCH2Br with
OH, Cl, NO3, O3 [3–6], respectively, which indicating that the dom-
inant atmospheric loss pathway for allyl bromide may be reaction
with OH radical. Up to date, only one experimental kinetic study
have been reported the reaction of OH with CH2@CHCH2Br. In
2003, Albaladejo and Ballesteros [3] measured the rate constant
of the reaction OH þ CH2 @CHCH2 Br ! products to be
(3.6 ± 1.5)  1012  exp(3783 ± 964/RT) cm3 molecules1 s1 at
P = 100 Torr and in the temperature range 228–388 K using the
pulsed laser photolysis/laser-induced fluorescence technique.
However, the detailed mechanisms of the degradation products of
allyl bromide in atmosphere are unclear for the title reaction.
Therefore, in order to detailed understand mechanistic and kinetic
of the OH + CH2@CHCH2Br reaction and understand the chemical
reactivity of CH2@CHCH2Br with OH in the atmospheric conditions,
it is necessary to present the mechanistic and kinetic studies for the
reaction of OH with CH2@CHCH2Br in this work.

http://dx.doi.org/10.1016/j.comptc.2017.01.005
2210-271X/Ó 2017 Elsevier B.V. All rights reserved.
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126
2. Computational methods
Electronic structure calculations are performed with Gaussian 09
program package [7]. The optimized geometries and harmonic fre-
quencies of all the stationary points are obtained at the M06-2X
[8,9]/6-311++G(d,p) level. The nature of all stationary structure is
verified by harmonic vibrational frequency calculations, namely,
equilibrium species possess all real frequencies; transition states
(TS) possess only one imaginary frequency. The zero-point energy
(ZPE) corrections are obtained at the same level. The transition
states were subjected to intrinsic reaction coordinate (IRC) [10,11]
calculations to confirm connection with designated intermediates.
To prove the energy prediction, the CCSD(T) [12] method with the
cc-pVTZ basis set was used to calculate the single point energies
based on the M06-2X/6-311++G(d,p) optimized geometries.
We choose the important product channels to calculate the rate
constants using the variational transition-state theory (VTST) and
multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) theory
[13]. In the section of the kinetic calculations, we employed the
modified computer program written by Hou and Wang for the
OH with allyl bromide reaction [14], and this methodology has
been successfully used to deal with the complex reactions [15–19].
3. Results and discussion
The optimized structures of stationary points (the complex,
intermediates, transition states, reactant and products) are listed
in Figs. 1–3, along with the available experimental values, respec-
tively. As seen in Fig. 3, the calculated bond lengths and angles at
the M06-2X/6-311++G(d,p) level are in good agreement with
experimental data [20], indicating that the M06-2X/6-311++G(d,
p) method is suitable for predicting the geometry of the title reac-
tion. To clarify the reaction mechanism, the potential energy sur-
face (PES) for this reaction at CCSD(T)/cc-pVTZ//M06-2X/6-311++
G(d,p) is described in Fig. 4. The ZPE, relative energies, reaction
enthalpies and Gibbs free energy for all the stationary points are
listed in Table 1. Table S1 displays the harmonic vibrational fre-
quencies and the moment of inertia (au) of all species, respectively.
The frequencies of CH2CHOH, CH2CHBr, CH3CHO, CH2OH, CH2O,
CH3, H2O, HOBr and OH are in agreement with experimental data
[20]. Unless mentioned otherwise, the geometric parameters used
in the discussion are the M06-2X/6-311++G(d,p) results, and the
energies used are at the CCSD(T)/cc-pVTZ + ZPE level.
3.1. Reaction mechanism
As the OH radical can have either abstraction or addition/elim-
ination mechanism, two distinguishable type initial attacks have
been revealed for the radical–molecule reaction OH + CH2@CHCH2-
Br, namely, the attack on H (or Br) atom and the addition to the
C@C double bond (addition–isomerization–elimination). A detailed
discussion on the title reaction mechanisms is given as follows.
3.1.1. Initial association
The OH-allyl bromide surface is characterized by two bound
intermediates, denoted as IM1 and IM2. The initial step involves
the addition of the OH radical to the C atom of the C@C bond of
CH2@CHCH2Br, generating the relatively stable radicals IM1 (CH2-
OHCHCH2Br) and IM2 (CH2CHOHCH2Br), respectively. The reaction
coordinate is complicated by an initial energy minimum at CR1,
which is a weakly bound complex with a 2.38 kcal/mol barrier
to further rearrangement. This typical phenomenon is also pro-
posed by Singleton and Cvetanovic et al [21]. Therefore, the reac-
tion of OH with allyl bromide to form IM1 and IM2 is effectively
without barrier. After formed the CR1, the oxygen atom of the
115
OH radical should rotate and add to the carbon atom of C@C double
bond in CH2@CHCH2Br via TS1 and TS2 to form IM1 and IM2, and
the corresponding barrier heights are calculated to be 3.07 and
1.31 kcal/mol, respectively. The relative energy of TS1 is 1.76 kcal/-
mol higher than that of TS2, Moreover, the DG (298 K) data for the
OH addition to the central-carbon atom (TS2) is 1.22 kcal/mol
lower than that addition to the terminal-carbon atom (TS1) of
the C@C double bond. These results indicate that the center C-
addition is slightly preferred over the terminal C-addition addition.
As seen in Fig. 4 and Table 1, the formation of IM1 and IM2 are
thermodynamically favorable. In the following part, we will focus
on discussing the formation pathways of various products which
associated with IM1 and IM2, respectively.
3.1.2. The unimolecular reaction of IM1
3.1.2.1. The CH2OH radical formation channel. Clearly, from IM1
(29.32), there are two feasible pathways to form P1 (CH2OH
+ CH2CHBr). They can be written as follows
PathP1ð1ÞR ! CR1 ! IM1 ! IM3 ! P1ðCH2 OH þ CH2 CHBrÞ
PathP1ð2ÞR ! CR1 ! I M1 ! IM4 ! P1ðCH2 OH þ CH2 CHBrÞ
IM1 can undergo a 1,2-Br shift to form IM3 (CH2OHCHBrCH2) via
transition state TS3 as shown in Path P1(1), or 1,2-H shift to form
IM4 (CH2OHCH2CHBr) via transition state TS4 as shown in Path
P1(2), respectively. Finally, both IM3 and IM4 can dissociate to P1
via CAC bond rupture corresponding transition state TS5 and TS6,
respectively. For IM1 ? P1 conversion, two barriers must be sur-
mounted in Path P1(1), which are 1.60 and 32.53 kcal/mol for the
steps of IM1 ? IM3 and IM3 ? P1, respectively, it should be noted
that the barrier of IM1 ? IM3 is the lowest barrier among all the
subsequent reaction channels of IM1 and IM2; while in Path P1
(2), the barriers are 43.64 (IM1 ? IM4) and 28.13 (IM4 ? P1) kcal/-
mol, respectively. Due to the higher isomerization barrier, we
expect that Path P1(2) should be less competitive with Path P1(1).
3.1.2.2. The CH2O radical formation channel. The hydrogen atom of
the OH group in IM1 is migrating to the C-central atom via TS7
to form another intermediate IM5 (CH2OCH2CH2Br). The barrier
height for IM1 ? IM5 is about 33.76 kcal/mol, which is 9.88 kcal/-
mol lower than TS4, and 32.16 kcal/mol higher than TS3. Subse-
quently, IM5 decomposes to form the final products P2 (CH2O
+ CH2CH2Br) via transition state TS8. The formation pathway of
P2 can be written as
PathP2R ! CR1 ! IM1 ! IM5 ! P2ðCH2 O þ CH2 CH2 BrÞ
The barrier height for this step is 17.12 kcal/mol. However, TS8 is
still lower than the reactants by 6.04 kcal/mol and TS1 by
6.73 kcal/mol, which indicating that P2 is easily yielded once IM5
is formed by increasing temperatures.
3.1.2.3. The CH2Br radical formation channel from IM1. Starting from
IM1, only one feasible channel is associated with the formation of
CH2Br radical, which can be written as
PathP3ð1ÞR ! CR1 ! IM1 ! IM6 ! P3ðCH2 Br þ CH2CHOHÞ
IM1 can isomerize to IM6 (CHOHCH2CH2Br) via a triangular struc-
ture transition state TS9. The barrier height of TS9 is 39.10 kcal/mol
with respect to IM1, which is 5.34 kcal/mol higher than TS7 and
37.50 kcal/mol higher than TS3, as well as higher than TS1
9.09 kcal/mol. IM6, -30.36 kcal/mol relative to the initial reactants,
breaks the CAC bond to give rise to P3 (CH2Br + CH2CHOH) via TS10
surmounting a 29.12 kcal/mol barrier height. Evidently, the rate-
determining step for the formation of P3 in Path P3(1) is the H-
shift step, i.e., IM1 ? TS9 ? IM6, because the barriers for the
entrance and decomposition steps TS1 and TS10 are both lower
116 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126

Fig. 1. Optimized geometries of species which connected to IM1 for the reaction of the CH2@CHCH2Br + OH reaction at M06-2X/6-311++(d,p) level.

than TS9. Moreover, due to higher isomerization barriers, this path- 3.1.2.4. The H-atom formation channel from IM1. There are three
way should not play an important role at low and moderate tem- feasible H-atom formation pathways from IM1, which can be
peratures, as confirmed by the kinetic calculation. depicted as
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126 117

Fig. 2. Optimized geometries of species which connected to IM1 for the reaction of the CH2@CHCH2Br + OH reaction at M06-2X/6–311++(d,p) level.

PathP4R ! CR1 ! IM1 ! P4ðH þ CHOHCHCH2 BrÞ PathP5ð2ÞR ! CR1 ! IM1 ! IM6 ! P5ðH þ CH2 BrCH2 CHOÞ

PathP5ð1ÞR ! CR1 ! IM1 ! IM5 ! P5ðH þ CH2 BrCH2 CHOÞ The IM1 ? IM5 and IM1 ? IM6 in Path P5(1) and Path P5(2) are
two hydrogen migration processes, which are the same as that in
118 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126

Fig. 3. Optimized geometries of reactants and products for the reaction of the CH2@CHCH2Br + OH reaction at M06-2X/6-311++(d,p) level. Bond distances are in angstroms,
and angles are in degrees. The values in italics are experimental data from ref 20.

Path P2 and Path P3(1), respectively. IM1, IM5 and IM6 can elimi-
nate H atom to form two different products P4 (H + CHOHCHCH2Br)
and P5 (H + CHOCH2CH2Br) via TS11, TS12 and TS13 via surmount-
ing 35.66, 23.27 and 35.68 kcal/mol energy barriers, respectively.
The relative energy of TS11 is 1.90 kcal/mol higher than that of
the rate-determining transition state TS7 in Path P5(1), and is
3.44 kcal/mol lower than that of the rate-determining transition
state TS9 in Path P5(2), respectively. Therefore, in view of the rela-
tive energies of rate-determining transition states and the simplic-
ity, the pathway of Path P5(2) cannot compete with Path P4 and
Path P5(1).
3.1.3. The unimolecular reaction of IM2
3.1.3.1. The CH2Br radical formation channel. For the CH2Br radical
formation channels, two reaction scenarios are possible from IM2
Path P3ð2Þ R ! CR1 ! IM2 ! P3 ðCH2 Br þ CH2 CHOHÞ
Path P6 R ! CR1 ! IM2 ! IM7 ! P6ðCH2 Br þ CH3 CHOÞ
One is the direct decomposition of IM2 to the final products P3 via
transition state TS14. This CAC bond fission barrier is quite low, i.e.,
28.88 kcal/mol, which is the lowest barriers on the PES from IM2.
Therefore, this formation of P3 channel should be the dominant
pathway of IM2.
The other minor reaction channel of IM2 involves the forma-
tion of another local minimum IM7 (CH3CHOCH2Br) via a 1,3-H
shift transition state TS15. The barrier for this isomerization
channel is 32.46 kcal/mol, which is 3.58 kcal/mol higher than that
of TS14. After IM7 is formed, the CAC bond can dissociate to P6
(CH2Br + CH3CHO) involved transition state TS16. This cleavage
process needs to surmount 15.56 kcal/mol barrier. TS16 is about
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126 119

Fig. 4. The profile of PES for the CH2@CHCH2Br + OH reaction at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level, (a) terminal-C addition (b) central-C addition (c)
abstraction, respectively.

8.98 kcal/mol lower than the reactants and 12.62 kcal/mol lower ization barrier of IM2 ? TS15 ? IM7 makes the pathway Path
than TS15, therefore, once IM7 is generated, P6 is easily yielded P6 far from competitive with pathway Path P3(2) under normal
by increasing temperatures. However, the rather higher isomer- conditions.
120 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126

Table 1
Relative Energies(DE), Reaction Enthalpies(DH) and Gibbs Free Energy(DG) at 298 K for all the species in the CH2@CHCH2Br + OH reaction (energies in kcal/mol).

Species ZPE DE a DEb DH0298 b DG b

R:(CH2@CHCH2Br + OH) 0.00 0.00 0.00 0.00 0.00

P1:(CH2OH + CH2CHBr) 50.21 6.82 5.67 5.78 8.04
P2:(CH2O + CH2CH2Br) 49.79 15.04 13.92 13.95 15.90
P3:(CH2Br + CH2CHOH) 50.08 10.36 9.45 9.54 11.92
P4:(H + CHOHCHCH2Br) 48.41 1.86 1.21 1.20 4.06
P5:(H + CHOCH2CH2Br) 47.89 8.07 6.70 6.67 4.06
P6:(CH2Br + CH3CHO) 49.35 20.06 20.14 20.02 22.98
P7:(CH3 + CH2BrCHO) 48.40 15.66 15.99 15.69 16.70
P8:(CH3 + CHOHCHBr) 49.00 11.82 11.06 10.88 11.48
P9:(H + CH2COHCH2Br) 47.98 2.91 0.61 0.62 2.34
P10:(H + CH3COCH2Br) 47.51 13.48 11.68 11.48 9.26
P11:(H + CH3COHCHBr) 47.57 6.96 4.76 4.58 1.92
h-P1:(CH2CHCHBr + H2O) 49.67 32.28 31.42 31.22 32.02
h-P2:(CH2CCH2Br + H2O) 49.47 12.86 10.28 9.82 11.28
h-P3:(CHCHCH2Br + H2O) 49.79 6.18 4.12 3.79 4.98
Br-P1:(CH2CHCH2 + HOBr) 49.76 7.13 7.36 5.60 11.14
CR1 51.69 4.77 2.38 2.64 5.21
IM1 54.55 33.50 29.32 30.35 20.93
IM2 53.61 32.50 28.82 29.87 19.87
IM3 54.32 34.73 30.52 31.66 21.40
IM4 54.33 30.86 27.97 28.96 19.42
IM5 54.26 26.59 23.16 24.52 14.41
IM6 54.53 34.22 30.36 31.55 21.49
IM7 53.36 27.69 24.54 25.49 16.26
IM8 53.86 33.63 30.91 31.90 22.12
IM9 54.01 45.79 40.10 40.82 31.88
TS1 51.76 0.76 0.69 0.08 8.69
TS2 51.94 2.54 1.07 2.03 7.47
TS3 54.23 32.74 27.72 29.09 18.66
TS4 51.16 10.04 14.32 13.34 22.86
TS5 51.60 1.14 2.01 1.13 10.52
TS6 51.93 3.14 0.16 0.71 8.34
TS7 51.68 2.18 4.44 2.96 13.35
TS8 51.94 8.70 6.04 7.17 2.52
TS9 51.33 1.72 9.78 8.55 18.46
TS10 51.82 3.97 1.24 2.04 6.60
TS11 49.34 3.35 6.34 5.31 15.14
TS12 49.16 3.15 0.11 1.09 8.90
TS13 48.87 1.88 5.32 4.30 13.89
TS14 51.53 2.61 0.06 0.80 8.50
TS15 51.16 1.78 3.64 2.10 12.93
TS16 51.78 11.03 8.98 9.98 0.62
TS17 51.38 9.44 7.24 8.23 1.36
TS18 50.80 8.88 11.78 10.42 20.87
TS19 51.13 2.52 0.58 1.39 8.02
TS20 48.98 4.54 6.62 5.52 15.60
TS21 48.80 5.49 3.10 4.14 5.54
TS22 50.92 1.54 6.82 5.70 15.70
TS23 48.44 3.27 0.78 1.63 7.59
TS24 49.09 0.08 2.10 1.02 11.16
h-TS1 48.74 0.12 0.69 0.09 8.28
h-TS2 48.63 2.58 3.58 2.90 11.44
h-TS3 48.26 4.68 5.98 5.36 13.81
Br-TS1 51.12 12.68 11.75 11.15 19.93
a
M06-2X/6-311++G(d,p) level.
b
CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level.

3.1.3.2. The CH3 radical formation channel. For the CH3 radical for-
mation channels, two pathways are energetically possible, which
can be depicted as:
Path P7 R ! CR1 ! IM2 ! IM7 ! P7ðCH3 þ CH2 BrCHOÞ
Path P8 R ! CR1 ! IM2 ! IM8 ! P8ðCH3 þ CHOHCHBrÞ
The formation of IM7 is the same as that in Path P6. Subsequently,
IM7 can further decompose to form P7 (CH3 + CH2BrCHO) via TS17,
as in Path P7. The barrier for the step of IM7 ? P7 conversion is
17.30 kcal/mol. This bond cleavage path is exothermic by
15.69 kcal/mol. Compared with the formation of P6, P7 are less
stable than P6. Furthermore, the barrier height of TS17 is 1.74 kcal/-
mol higher than of TS16. Therefore, the formation of P6 channel
occurs more preferentially than the formation of P7 channel.
In Path P8, IM2 can transform to IM8 (CH3CHOHCHBr) via a
four-membered-ring transition state TS18. The barrier height is
40.60 kcal/mol, which is higher than TS14 by 11.72 kcal/mol and
TS15 by 8.14 kcal/mol, respectively. IM8, 30.91 kcal/mol relative
to the initial reactants, can break the CAC bond to give rise to P8
(CH3 + CHOHCHBr) via TS19. The barrier height is 30.33 kcal/mol,
which is 13.03 kcal/mol higher than that of the IM7 ? P7 conver-
sion. These results indicate that the Path P8 occurs less favorable
than the Path P7.
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126
3.1.3.3. The H-atom formation channel. There are four H-atom for-
mation pathways through IM2 which can transform to the corre-
sponding product.
Path P9R ! CR1 ! IM2 ! P9 ðH þ CH2 COHCH2 BrÞ
Path P10ð1Þ R ! CR1 ! IM2 ! IM7 ! P10ðH þ CH3 COCH2 BrÞ
Path P10ð2Þ R ! CR1 ! IM2 ! IM9 ! P10ðH þ CH3 COCH2 BrÞ
Path P11 R ! CR1 ! IM2 ! IM8 ! P11ðH þ CH3 COHCHBrÞ
For the above four H-elimination pathways, which have the same
steps of R ? CR1 ? IM2, and subsequently, isomer IM2 transforms
to three different of products via four different reaction pathways.
(i) In Path P9, IM2 can take CAH bond rupture leading to P9 (H
+ CH2COHCH2Br) via TS20. The dissociation barrier is 35.44 kcal/-
mol. (ii) The formation pathways of IM7 have been discussed in pre-
vious sections (in Path P6). For brevity, we decide not to discuss
them again. IM7 can dissociate to P10 (H + CH3COCH2Br) via the
CAH bond rupture transition state TS21 as in Path P10(1). The rela-
tive energy of rate-determining transition states TS15 in Path P10(1)
is 2.98 kcal/mol lower than that of TS20 in Path P9, while 3.58 kcal/-
Fig. 5. Brief description of the progression on PES for the CH2@CHCH2Br + OH reaction.
121
mol higher than that of TS14 in Path P3(2). Therefore, in view of the
relative energies of rate-determining transition states and the sim-
plicity, we can conclude that Path P9 is less competitive than path-
ways Path P3(2) and P10(1), and Path P3(2) has priority over the
pathway Path P10(1). (iii) In Path P10(2), a successive 1,2-H-shift
and dissociation steps (IM2 ? IM9 ? P10) can also lead to product
P10 (H + CH3COCH2Br) via transition states TS22 and TS23. It is an
H-shift-H-elimination mechanism. Two high barriers need to be sur-
mounted from IM2 to P10, that is, 35.64 and 39.32 kcal/mol for
IM2 ? IM9 and IM9 ? P10 conversion, respectively. Because the
rate-determining energy barrier (39.32) of Path P10(2) is higher than
of Path P10(1) (32.46). Therefore, pathway Path P10(2) should be
less competitive than pathway Path P10(1). (iv) For Path P11, the for-
mation of IM8 is the same as that in Path P8. Subsequently, IM8
undergoes a H-elimination process to produce P11 (H + CH3-
COHCHBr) via TS24. The barrier for IM8 ? P11 conversion is
33.01 kcal/mol. Yet, the rate-determining energy barrier for Path
P11 is 40.60 kcal/mol, which is 5.16, 8.14 and 1.28 kcal/mol higher
than that of Path P9, Path P10(1) and Path P10(2), respectively.
Therefore, from the kinetic consideration, for the above mentioned
four H-elimination pathways, the order of reaction competition abil-
ities is Path P10(1) > Path P9 > Path P10(2) > Path P11.
122 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126

3.2. H-abstraction and Br-abstraction pathways

As shown in Fig. 5, there are four different direct H (or Br)

abstract pathways. The most favorable channel is the forming of
h-P1 (CH2CHCHBr + H2O) via h-TS1. The energy of h-TS1 is only Scheme 2.
0.69 kcal/mol higher than the reactants. The second and three
channels corresponds to hydrogen abstraction channel by OH from
the center C atom of -CH and -CH2 groups of CH2@CHCH2Br, lead-
ing to h-P2 (CH2CCH2Br + H2O) and h-P3 (CHCHCH2Br + H2O) via
transition states h-TS2 and h-TS3 with the barrier height of 3.58
and 5.98 kcal/mol which is 2.89 and 5.29 slightly higher than that
of h-TS1. The last pathway is abstracting the Br atom of CH2-
@CHCH2Br by OH radical to form the final product Br-P1 (HOBr
+ CH2CHCH2) via transition state Br-TS1. The calculated barrier
height for this process is 11.75 kcal/mol, which are 11.06, 8.17 Scheme 3.
and 5.77 kcal/mol higher than h-TS1, h-TS2 and h-TS3, respec-
tively. Moreover, the Gibbs energies (DG) of h-P2, h-P3 and Br-P1
are 20.74, 27.04 and 43.16 kcal/mol higher than that of h-P1, aa Q– –
t Qr
kP2 ðT; PÞ ¼ eEa =RT
respectively. Obviously, the most feasible abstract channel is the h Q CH2 @CHCH2 Br Q OH
formation of h-P1 among these four abstract pathways. Z 1
k8 ðEÞX 3 – –
 N a ðE– ÞeE =RT dE ð5Þ
0 X 4
3.3. Kinetic calculation
aa Q– –
t Qr
The kinetic calculation for the important reaction routes of the kP4 ðT; PÞ ¼ eEa =RT
h Q CH2 @CHCH2 Br Q OH
OH + CH2@CHCH2Br reaction (Schemes 1–3) is calculated by using Z 1
the variational transition-state theory (VTST) and multichannel k6 ðEÞ – –
 Na ðE– ÞeE =RT dE ð6Þ
Rice-Ramsperger-Kassel-Marcus (RRKM) theory on the basis of 0 X4
energetics, frequencies and moments of inertia of various relevant With the following definition:
species. The reaction paths including in Schemes 1–3 are consid-
ered in the following calculation: X 1 ¼ k1 ðEÞ þ k2 ðEÞ þ k4 ðEÞ þ k6 ðEÞ þ x
where ‘‘⁄” represents the vibrational excitation of the interme-
diate (IMj). Steady-state assumption for energized intermediate X 2 ¼ k2 ðEÞ=ðk3 ðEÞ þ k7 ðEÞ þ xÞ
(IMj⁄) leads to the following expressions (the detailed calculation
processes are given in the Supporting information (Note S1)): X 3 ¼ k4 ðEÞ=ðk5 ðEÞ þ k8 ðEÞ þ xÞ
For Scheme 1:
X 4 ¼ X 1  k3 ðEÞ  X 2  k5 ðEÞ  X 3
aa Q– –
t Qr
kIM1 ðT; PÞ ¼ eEa =RT For Scheme 2:
h Q CH2 @CHCH2 Br Q OH
Z 1
x – – aa Q– –
t Qr
 N a ðE– ÞeE =RT dE ð1Þ kIM2 ðT; PÞ ¼ eEa =RT
0 X4 h Q CH2 @CHCH2 Br Q OH
Z 1
x – –
aa Q– –  Na ðE– ÞeE =RT dE ð7Þ
t Qr X1
kIM3 ðT; PÞ ¼ eEa =RT 0
h Q CH2 @CHCH2 Br Q OH
Z 1
X2x – – aa Q– –
t Qr
 Na ðE– ÞeE =RT dE ð2Þ kP3 ðT; PÞ ¼ eEa =RT
0 X4 h Q CH2 @CHCH2 Br Q OH
Z 1
k2 ðEÞ – –
aa Q– –  Na ðE– ÞeE =RT dE ð8Þ
t Qr X1
kIM5 ðT; PÞ ¼ eEa =RT 0
h Q CH2 @CHCH2 Br Q OH
Z 1
X3x – – aa Q– –
t Qr
 Na ðE– ÞeE =RT dE ð3Þ kP9 ðT; PÞ ¼ eEa =RT
0 X 4 h Q CH2 @CHCH2 Br Q OH
Z 1
k3 ðEÞ – –
aa Q– –  Na ðE– ÞeE =RT dE ð9Þ
t Qr X
kP1 ðT; PÞ ¼ eEa =RT 0 1
h Q CH2 @CHCH2 Br Q OH
Z 1 With the following definition:
k7 ðEÞX 2 – –
 Na ðE– ÞeE =RT dE ð4Þ X 1 ¼ k1 ðEÞ þ k2 ðEÞ þ k3 ðEÞ þ x
0 X 4

Scheme 1.
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126 123

The microcanonical rate constant is calculated using the RRKM
theory as follows:
ki ðEÞ ¼ ai C i N i ðE–
i Þ=hqj ðEj Þ
In the above equations, aa is the statistical factor for the reac-
tion path a, and ai is the statistical factor (degeneracy) for the ith
reaction path; Ea is the energy barrier for the reaction step a. Q OH
and Q CH2 @CHCH2 Br are the total partition function of OH and CH2-
@CHCH2Br, respectively; Q – –
t and Q r are the translational and rota-
tional partition functions of entrance transition state, respectively;
N a ðE– Þ is the number of state for the association transition state
with excess energy E– above the association barrier. ki ðEÞ is the
energy-specific rate constant for the ith channel and Ci is the ratio
of the overall rotational partition function of the TSi and IMj; N i ðE–
i Þ
is the number of states at the energy above the barrier height for
transition state i; qj ðEj Þ is the density of states at energy Ej of the
intermediate. The density of states and the number of states are
calculated using the extended Beyer-Swinehart algorithm [22,23].
Where x = bcZLJ[M] and bc is the collision efficiency, which is calcu-
lated using Troe’s weak collision approximation [22] with the
energy transfer parameter hDEi, The simple expression for colli-
ð7Þ
sional energy transfer (hDEi) [24,25] is
bc hDEi
ffi
1  bc1=2 F E kT
This expression holds nearly exactly at the weak collision limit
hDEi  FEkT for all collision models [24,25]. The factor FE is set
to 1.0 empirically. The average energy transfer per collision, i.e.,
hDEi, is unknown and cannot be calculated quantitatively. In con-
sideration of the experimental rate constants, it is found that the
values around 100 cm1 for hDEi should be reasonable to calculate
the rate constants. ZLJ is the Lennard-Jones collision frequency. The
collision efficiency is estimated using the Lennard-Jones potential
(V(r) = 4e[(r/r)12  (r/r)6]) by fitting the interaction energies calcu-
lated at the M06-2X/6-311++G(d,p) level for IM1. . .He and

Fig. 6. Arrhenius plots of the total and individual rate constants for the CH2@CHCH2Br + OH reaction at 100 Torr He.

Fig. 7. Branching ratios for the CH2@CHCH2Br + OH reaction, which correspond to Fig. 3 with a pressure of 100 Torr He.
124 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126
IM2. . .He. It is estimated that (e = 42.38 K, r = 2.82 Å) for IM1. . .He
and (e = 27.81 K, r = 2.86 Å) for IM2. . .He, and [M] is the concentra-
tion of the bath gas M (He). The weak collision approximation is
used for the intermediate.
The rate coefficients for the direct hydrogen abstraction routes
can be readily obtained using the conventional transition-state
theory, viz.:
kB T Q–
kabs ðTÞ ¼ j1 TS
eE1 =ðRTÞ
h Q CH2 @CHCH2 Br Q OH
where j1 is the tunneling factor, kB and h are Boltzmann and Planck
constants, respectively. Q –
TS , Q CH2 @CHCH2 Br and Q OH are the h-TS1 (h-
TS2 or h-TS3), CH2@CHCH2Br and OH partition functions, respec-
tively. E1 is the energy barrier of h-TS1 (h-TS2 or h-TS3). The
unsymmetrical Eckart potential model is employed to estimate j1
[26,27].
The rate coefficients are calculated as a function of temperature
in the range of 200–3000 K. Arrhenius plots of the total and indi-
vidual rate constants at the whole temperature range and at the
pressure of 100 Torr, He are shown in Fig. 6, together with some
of the available experimental data for comparison between our
computed and the available experimental data. The calculated
results reveal that our calculated total rate constants at 228–
388 K are in good agreement with the available experimental val-
Fig. 8. Calculated overall rate coefficients for the CH2@CHCH2Br + OH reaction in a
pressure range of 1014–1014 Torr of He bath gas at T = 298 K, 1000 K and 3000 K,
respectively.
Fig. 9. Branching ratios for the CH2@CHCH2Br + OH reaction n a pressure range of 1014–1014 Torr of He bath gas at T = 298 K, 1000 K and 3000 K, respectively.
ues. The product branching ratios for the title reaction are shown
in Fig. 7. As can be seen from Fig. 7, the fraction of the IM3 depends
strongly on temperature. i.e., from 96.7 at 200 K, 37.1% at 700 K,
and decreasing to 2.28% at 1200 K. Temperature-dependence of
the fraction of the H-abstract (from CH2Br group) and P1 (CH2-
OH + CH2CHBr) are more complicated. For H-abstract, first, it shar-
ply rises with temperature and reaches a maximum of 66.3% at
about T = 2200 K, and then almost linearly decreases when tem-
perature increase further. Similar changes occur for P1, the fraction
of P1 sharply rises with increasing temperatures first at 200–900 K,
from 0 at 200 K up to maximal point of 44.9% at 900 K, but drops at
T P 1000 K, from 44.1% at 1000 K down to 1.45% at 3000 K. From
Fig. 7, we can see that P1 is dominant products at 700–1000 K;
h-P1 and IM3 are the major products at T P 1000 K and 200–
700 K, respectively.
Meanwhile, we have also provided the rate constants in the
temperature range of 200–3000 K at atmospheric pressure
P = 760 Torr as presented in Fig. S1, At T = 298 K and P = 760 Torr,
the total rate constant is 1.77  1011 cm3 molecule1 s1. For
practical use, the predicted total and important individual rate
constants are fitted to a modified three parameter Arrhenius
expression. The rate constants for the total (ktot) and the forma-
tions of kIM1, kIM2, kIM3, kh-TS1 and kP1 in units of cm3 molecule1
s1 are presented, respectively, as follows:
K tot ¼ 5:46  1014 T 3:27 expð6:08=TÞð200 6 T 6 500Þ
K tot ¼ 8:79  1012 T 0:99 expð0:76=TÞð500 < T 6 3000Þ
K IM1 ¼ 4:53  1017 T 3:76 expð2:14=TÞð200 6 T 6 3000Þ
K IM2 ¼ 1:58  106 T 2:58 expð119:95=TÞð200 6 T 6 500Þ
K IM2 ¼ 5:62  1012 T 1:36 expð2569:62=TÞð500 6 T 6 3000Þ
K IM3 ¼ 3:15  109 T 1:02 expð171:32=TÞð200 6 T 6 3000Þ
K hTS1 ¼ 2:14  1014 T 1:25 expð3289:26=TÞð1000 6 T 6 3000Þ
kP1 ¼ 1098:88T 3:92 expð5561:20=TÞð200 6 T 6 1400Þ
kP1 ¼ 5:04  107 T 1:46 expð346:04=TÞð1400 < T 6 3000Þ
No pressure-dependence studies for the CH2@CHCH2Br + OH reac-
tion were reported previously. The total rate constant and branch-
ing ratio have been calculated in the wide pressure range of
 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126 125

Table 2
The parameters for the first 10 excited states of all the intermediates in the title reaction.

Species parameters Excited state

1 2 3 4 5 6 7 8 9 10
CR1 k (nm) 3019.22 329.77 292.99 263.11 241.37 238.02 219.94 215.28 202.38 197.27
f 0.0000 0.0007 0.0712 0.0114 0.0057 0.0003 0.0000 0.0000 0.0049 0.0020
Excitation energies(eV) 0.4106 3.7598 4.2316 4.7123 5.1368 5.2090 5.6372 5.7592 6.1262 6.2849
IM1 k(nm) 333.76 332.29 266.49 257.91 239.00 217.07 214.91 209.51 208.13 206.72
f 0.0003 0.0017 0.0014 0.0369 0.0340 0.0023 0.0141 0.0004 0.0118 0.0058
Excitation energies(eV) 3.7148 3.7312 4.6525 4.8073 5.1875 5.7117 5.7691 5.9178 5.9572 5.9976
IM2 k(nm) 244.00 231.03 228.16 221.43 216.67 209.58 207.66 202.27 200.33 197.15
f 0.0009 0.0167 0.0013 0.0011 0.0068 0.0007 0.0017 0.0142 0.0012 0.0064
Excitation energies(eV) 5.0814 5.3666 5.4342 5.5992 5.7223 5.9158 5.9705 6.1298 6.1889 6.2889
IM3 k(nm) 327.32 317.37 271.59 237.03 226.91 217.76 208.15 205.98 204.39 199.06
f 0.0011 0.0003 0.0360 0.0044 0.0108 0.0581 0.0055 0.0007 0.0024 0.1039
Excitation energies(eV) 3.7878 3.9066 4.5651 5.2307 5.4640 5.6937 5.9564 6.0191 6.0659 6.2285
IM4 k(nm) 313.48 258.84 243.31 228.69 224.86 222.38 213.69 199.29 195.31 194.37
f 0.0036 0.0000 0.0018 0.0020 0.0104 0.0521 0.0177 0.0001 0.0001 0.0049
Excitation energies(eV) 3.9551 4.7900 5.0958 5.4214 5.5140 5.5754 5.8021 6.2212 6.3480 6.3787
IM5 k(nm) 3193.25 338.18 268.22 262.03 221.15 217.74 208.45 202.62 199.57 190.49
f 0.0001 0.0007 0.0042 0.0037 0.0001 0.0001 0.0191 0.0004 0.0010 0.0036
Excitation energies(eV) 0.3883 3.6662 4.6225 4.7316 5.6064 5.6941 5.9479 6.1190 6.2125 6.5087
IM6 k(nm) 298.65 278.97 263.99 243.15 238.36 222.02 220.31 216.80 211.64 211.00
f 0.0046 0.0041 0.0065 0.0204 0.0032 0.0008 0.0003 0.0012 0.0030 0.0026
Excitation energies(eV) 4.1514 4.4444 4.6966 5.0991 5.2016 5.5844 5.6278 5.7188 5.8583 5.8761
IM7 k(nm) 3529.40 355.72 289.89 285.12 220.88 218.60 217.47 201.70 199.72 198.47
f 0.0001 0.0014 0.0004 0.0025 0.0047 0.0140 0.0015 0.0014 0.0022 0.0057
Excitation energies(eV) 0.3513 3.4854 4.2769 4.3485 5.6133 5.6717 5.7013 6.1470 6.2078 6.2470
IM8 k(nm) 305.91 262.98 241.58 227.33 220.91 214.33 202.38 200.95 199.02 193.66
f 0.0025 0.0009 0.0013 0.0145 0.0324 0.0052 0.0032 0.0042 0.0006 0.0002
Excitation energies(eV) 4.0530 4.7145 5.1322 5.4540 5.6125 5.7847 6.1262 6.1700 6.2299 6.4021
IM9 k(nm) 428.97 420.28 329.02 306.59 254.42 240.54 235.72 228.10 223.36 210.88
f 0.0003 0.0003 0.0399 0.0118 0.0006 0.1041 0.1786 0.0161 0.0890 0.0001
Excitation energies(eV) 2.8903 2.9500 3.7683 4.0439 4.8732 5.1545 5.2599 5.4354 5.5508 5.8794

1014–1014 Torr at the selected temperatures 298, 1000 and 3000 K,
respectively. The calculated results were listed in Figs. 8 and 9,
respectively. It can be seen from Fig. 8 that there was a typical falloff
behavior for the complex forming reactions. With the temperature
increasing, the falloff range shifts to the low pressure. At 298 K,
the falloff region for the total rate constants is 103 to 101 Torr. At
1000 and 3000 K, the falloff region moves to lower pressures
(106 to 102 Torr and 109 to 104 Torr, respectively). Meanwhile,
the individual rate constants are sensitive to the pressure. Fig. 9
reveals that at 298 K, the major products are IM3 (CH2OHCHBrCH2)
at lower and moderate pressures (e.g., P < 102 Torr), at the higher
pressures, the stabilization of intermediate IM1(CH2OHCHCH2Br)
becomes dominant; at 1000 K, the production of P1(CH2OH + CH2-
CHBr) and h-P1 (CH2CHCHBr + H2O) are the major reaction channel
at P < 1 Torr, h-P1 (CH2CHCHBr + H2O) and IM3 are the major prod-
ucts at 1–104 Torr, At higher pressure, the dominant channel is the
stabilization of the IM1(CH2OHCHCH2Br) and h-P1 (CH2CHCHBr
+ H2O); the hydrogen abstraction channel from the ACH2Br group
of CH2@CHCH2Br is the dominant channel at the whole pressure
range at 3000 K, respectively. All of these theoretical predictions
must await future experimental verification.
3.4. UV–visible spectroscopy
The Ultraviolet visible spectra analysis of the important species
in the OH + CH2@CHCH2Br reaction has been conducted using the
time dependent density functional theory (TD-DFT) at the M06-
2X/6-311++G(d,p) level based on the ground-state optimized
structures. The fluorescent properties of a molecule can be influ-
enced by its light-absorption process. There are many stable inter-
mediates generated in the title reaction. In order to get their
photolysis information in the sunlight, the calculated wavelength
of absorption (k), oscillator strength (f) and the excitation energies
for first ten excited states of are illustrated in Table 2. It is well
known that when the excitation energies above 4.13 eV (about
300 nm), the compound is regarded to be photolyzed in the sun-
light. It can be seen from Table 2 that the first excitations of IM1
(CH2(OH)CHCH2Br), IM2(CH2CH(OH)CH2Br), IM3(CH2OHCHBrCH2),
IM4(CH2OHCH2CHBr), IM6 (CHOHCH2CH2Br), IM8 and IM9, hap-
pen at 333 nm (3.7148 eV), 244 nm (5.0814 eV), 327 nm
(3.7878 eV), 313 nm (3.9551 eV), 298 nm (4.1514 eV), 305 nm
(4.0530 eV) and 428 nm (2.8903 eV), respectively. Moreover, all
the oscillator strengths of the excited states of the above species
are above 0.0002, which indicated that they could easily undergo
photolysis in the sunlight. Therefore, they have received significant
attention in the photochemistry of the brominated organic com-
pounds produced by CH2@CHCH2Br + OH reaction, specifically
their wave-length dependence.
4. Conclusions
The potential energy surfaces (PES) for the CH2@CHCH2Br + OH
reaction were systematically characterized at both the M06-2X and
CCSD(T) levels. The calculated results revealed that the CH2-
@CHCH2Br + OH reaction takes place via the abstraction and addi-
tion/elimination mechanisms. The barrierless interaction of the
two reactants leads to a pre-reactive complex, which bifurcates
into two different pathways leads to two energy-rich adducts
(IM1 and IM2) with excess energy, which can react further to
decomposition or rearrangements. The variational transition state
theory and the RRKM theory is employed to calculated the kinetics
126 Y. Zhang et al. / Computational and Theoretical Chemistry 1102 (2017) 114–126
of the title reaction over the temperature range of 200–3000 K and
the pressure range of 1014–1014 Torr. It is concluded that the sta-
bilization of the adduct IM3 (CH2OHCHBrCH2) and P1 (CH2OH
+ CH2CHBr) dominate the reaction at 200–700 K and 700–1000 K,
respectively. The rate constant shows a weak temperature depen-
dence. The abstraction pathway from the ACH2Br group of CH2-
@CHCH2Br becomes dominant at higher temperatures. The rate
constant shows a strong temperature dependence. Meanwhile,
the total rate constant exhibits an obvious falloff behavior. Time-
dependent DFT (TD-DFT) calculations indicate that IM1-IM4, IM6,
IM8 and IM9 take photolysis easily in the sunlight, once they are
generated.
Acknowledgments
This work is supported by the National Natural Science Founda-
tion of China (No. 21507027), the Youth Fund Project of HuBei
Provincial Department of Education (Q20132501) and Hubei Key
Laboratory of Pollutant Analysis & Reuse Technology Open Fund
(PA160204).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.comptc.2017.01.
005.
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