Ab Initio Study of the CH3 + O2 Reaction: Kinetics,

Mechanism and Product Branching Probabilities

Rongshun Zhu, C.–C. Hsu and M. C. Lin*
Department of Chemistry, Emory University, Atlanta, Georgia 30322

Abstract
The reaction of CH3 radical with molecular O2 has been investigated by ab initio
molecular orbital theory and variational transition state theory calculations. The detailed
potential energy surfaces (PES), including the crossing seams between the PES, located by
means of the intrinsic reaction coordinate (IRC) approach are presented. The rate constants for
the association and product formation channels have been calculated and compared with the
experimental data. The branching probabilities for channels (b) and (c) producing CH2O + OH
and CH3O + O, respectively, are compared. Under atmospheric- pressure conditions, channel (b)
is predicted to be dominant below 2000 K with the rate constant kb = 1.14µ10-22T2.86 exp (-
5115.4/T) cm3molecule-1 s-1. Over 2000 K, channel (c) becomes competitive; its rate constant
could be represented by kc= 1.01µ10-16T1.54exp(-13275.7/T) cm3molecule -1 s-1 in the temperature
range of 1000~3000 K. In addition, the most exothermic products, CHO + H2O, were found to
be kinetically inaccessible because of the large barrier, 47.4 kcal/mol above the reactants.

-------------------------------------------------
* Corresponding author: chemmcl@emory.edu
1. Introduction
The oxidation of CH3, the most stable alkyl radical, by molecular oxygen is one of the
most important reactions in the combustion of hydrocarbons and hence has been the subject of
numerous experimental and theoretical studies.1-44 The reaction has been shown to occur mainly
through three channels:
CH3 + O2 Ø CH3O2 (a)
Ø CH2O + OH (b)
Ø CH3O + O (c)
There are, however, two references,26,27 which reported the possibility of the following
most exothermic product channel:
CH3 + O2 Ø HCO + H2O (d)
The association process (channel a) is pressure-dependent and dominant at temperatures
below 1000 K.28-44 At higher temperatures, channels (b) and (c), which are chain-branching
reactions, become important and possibly competitive. The degree of competition between the
two reactions has been a subject of much controversy over the years. One of the major goals of
the present study is to quantitatively characterize channel (b) theoretically. Experimentally, it has
been difficult to determine the product branching ratios quantitatively for these two competitive
channels on account of the fact that the reactions are slow and only high-temperature
measurements above ~1300 K in shock waves could produce some meaningful data. Under
high-temperature conditions, however, fast secondary radical reactions generated by the
fragmentation of CH3, CH3O and CH2O and their reactions with H, O and OH rapidly

1
overwhelm the primary process of interest, CH3 + O2, rendering an accurate determination of the
total rate constant and product branching probabilities very difficult. This difficulty has been
partially overcome by the development of sensitive and reliable diagnostics such as atomic
resonance absorption spectroscopy (ARAS)11,15,17,20,21 resonance absorption spectroscopy
(LRAS)15, 17, 21 which makes kinetic measurements under highly diluted conditions (to minimize
secondary reactions) possible. Recent measurements by the combination of these techniques
aided by kinetic modeling of measured data have led to a near convergence for the rate constant
of channel (c).17,20,21 These and earlier results will be cited and compared with our predicted
values later.
Theoretically, the key feature of the potential energy surfaces (PES) of the CH3 + O2
reaction has been investigated by Walch23 using the complete active space SCF/internally
contracted configuration interaction (CASSCF/ICCI) method with the polarized double-zeta
basis set of Dunning and Hay.45 He qualitatively discussed the coupling between the initially
formed 2A” CH3OO species and the exit portion of the 2A’ surface leading to CH2O + OH. No
minimum corresponding to CH2OOH was found on the surface producing CH2O + OH in his
calculation. Green24 briefly studied this system using density functional theory (DFT) based on
DZVP and TZVP basis sets.46,47 Independently, Sicilia et al.25 investigated the reaction at the
UMP4//UMP2/DZP and QCISD(T)//UMP2/DZP levels of theory. Symmetry constraint and
surface coupling were not considered in these two studies, although the existence of the
CH2OOH intermediate was reported. None of these theoretical studies attempted to predict the
total reaction rate and product-branching ratios for the three channels (a-c) mentioned above; nor
did they rule out theoretically the possibility or impossibility of the most exothermic product
channel (d).
In the present work, we attempt to map out the complete PES for the system and carry out
detailed rate constant calculations for all accessible channels cited above on the basis of the
computed PES using a variational statistical method. The results of this comprehensive study are
presented herein.

2. Computational Methods
2.1 Ab initio calculations
The geometries of the reactants, intermediates, transition states, and products of the CH3
+ O2 reaction were optimized at the B3LYP/6-311G(d,p) (i.e., Becke’s three-parameter nonlocal
exchange functional48-50 with nonlocal correlation functional of Lee et al.51 The energies of all
species were calculated by the G2M52 method, which uses a series of calculations with
B3LYP/6-311G(d,p) optimized geometries to approximate the CCSD(T)/6-311+G(3df,2p) level
of theory, including a “higher level correction (HLC)” based on the number of paired and
unpaired electron. The total G2M energy with zero-point energy (ZPE) correction is calculated
as follows52:
E[G2M(RCC, MP2)] = E[RCCSD(T)/6-311G(d, p)] + ∆E(+3df, 2p) + ∆E(HLC) +
ZPE[B3LYP/6-311G(d, p)].
∆E(+3df, 2p) = E[MP2/6-311 + G(3df, 2p)] - E[MP2/6-311G(d, p)].
∆E(HLC) = -0.00525 nβ - 0.00019 nα;
where nα and nβ are the numbers of valence electrons, nα ≥ nβ. All calculations were carried out
with Gaussian 9853 and MOLPRO 9654 programs.

2
2.2 RRKM calculations
The rate constant and product branching ratios were computed with a microcanonical
variational RRKM (Variflex55) code which solves the master equation55-58 involving multi-step
vibrational energy transfers for the excited intermediate (CH3O2÷). The ab initio PES calculated
at the G2M level, to be discussed in the next section, was used in the calculation.
Similar to our previous calculation59 with the Variflex code, the component rates were
evaluated at the E, J-resolved level. The pressure dependence was treated by 1-D master equation
calculations using the Boltzmann probability of the complex for the J distribution. The master
equation was solved by an inversion based approach.55,56 In order to achieve convergence in the
integration over the energy range, an energy grain size of 100 cm-1 was used, this grain size
provides numerically converged results for all temperatures studies with the energy spanning
range from 15,000 cm-1 below to 64,900 cm-1 above the threshold. The total angular momentum
J covered the range from 1 to 241 in steps of 10 for the E, J-resolved calculation. For the
barrierless transition states, the Varshni potential60, 61
V(R) = De{1 - a exp[- b(R2 - R02)]}2 - De
was used to represent the potential energy along the individual reaction coordinate. In the above
equation, De is the bond energy excluding zero-point vibrational energies and a = R0/R, where R
is the reaction coordinate (i. e. the distance between the two bonding atoms, in the present case
C—O, or O—O) and R0 is the equilibrium value of R. For the tight transition states, the
numbers of states were evaluated according to the rigid-rotor harmonic-oscillator assumption.
3. Results and Discussion
3.1. Potential Energy Surfaces and Reaction Mechanism
The optimized geometries of the reactants, intermediates, transition states and products are
shown in Fig. 1; the potential energy diagram obtained at the G2M level is presented in Fig. 2;
the total and relative energies are compiled in Table 1 and the vibrational frequencies and
moments of inertia of all species are summarized in Table 2. As shown in Fig. 2, the CH3 + O2
reaction can occur by two association processes involving O2 in the two lowest electronic states.
The reaction of CH3 with the ground electronic state O2 (3 ∑ −g ) occurs barrierlessly to form the
CH3O2 (LM1) intermediate with 2A” symmetry. The association process is predicted to be
exothermic by 30.4 kcal/mol, which agrees excellently with the value determined by Slagle and
Gutman, 30.9 ± 0.9 kcalmol.62 In the 2A” CH3O2 state, there are two electrons doubly occupying
the in-plane 2p-like orbital of the terminal oxygen atom; therefore, the migration of a hydrogen
atom to the terminal oxygen atom is energetically unfavorable.23 However, the reaction can
proceed by breaking the O-O bond producing the CH3O + O products with an overall
endothermicity of 27.7 kcal/mol, to be compared with the experimental value, 28.7 kcal/mol.63 A
further discussion on the endothermicity will be made later because of its critical effect on the
predicted rate constant for this important product channel.
In the second association process, the reaction takes place by the interaction of the
electronically excited O2 (1Dg) with CH3 to form the electronically excited CH3O2 intermediate,
LM2, with 2A’ symmetry. The intermediate is more stable than the CH3 + O2 (3 ∑ −g ) reactants
by 9.2 kcal/mol. The association reaction was also found to occur barrierlessly without a well-
defined transition state. In the 2A’ state, there is only one electron occupying the in-plane 2p-like
orbital of the terminal oxygen atom; thus, the migration of a hydrogen atom to the oxygen atom
is favorable with this symmetry. The reaction can proceed further by elimination of OH as will
be discussed below. It should be noted that the predicted relative energy between the excited and
the ground state CH3 + O2 reactants is 26.3 kcal/mol, which is much larger than the experimental

3
value of the singlet-triplet energy difference, 22.5 kcal/mol.64 The G2-like methods52 predict the
heats of atomization of molecular oxygen in these two states rather poorly. By CASSCF, Walch
calculated the energy difference to be 24.6 kcal/mol.23
Decomposition of the CH3O2 intermediates: The excited LM1 formed by CH3 +
O2( ∑ −g ) can undergo decomposition via two transition states, TS2 and TS3. TS2 lies 68.8
3

kcal/mol above the intermediate with Cs symmetry, directly producing CH2O + OH by a

concerted H-migration/OH-elimination mechanism. Interestingly, the result of an IRC analysis
along both Cs and C1 symmetry paths shows that TS2 originates from LM1 having a cis-
HCOO/planar structure with Cs symmetry. TS3, however, has C1 symmetry; it is formed by H-
migration from one of the two equivalent C-H bonds in the staggered position with the O-O
bond to give the CH2OOH isomer, LM3, with a barrier of 59.8 kcal/mol. LM3 lies 18.5 kcal/mol
below the reactants; it fragments readily to produce CH2O + OH with a small barrier (7.2
kcal/mol) at TS4. LM3 can, inprinciple, also undergo H2O elimination producing the most
exothermic products, HCO + H2O, via TS5 with a large barrier of 65.9 kcal/mol. The large
barrier effectively rules out the possibility of this reaction step, despite its high exothermicity,
83.9 kcal/mol. As alluded to above, LM1 can also decompose directly by breaking the O-O bond
to give CH3O + O. This endothermic process occurs barrierlessly without a well-defined TS.
The large barriers at TS2 and TS3 also effectively prevent the decomposition of the 2A” CH3O2
intermediate, producing CH2O + OH directly over the 2A” PES.
The 2A’ CH3O2 intermediate, LM2, formed by the association of CH3 with O2 (1Dg),
however, can undergo a concerted H-migration/OH-elimination reaction readily (see Fig. 2)
producing CH2O + OH via TS1. This channel is computed to be exothermic by 53.5 kcal/mol,
compared to 53.2 kcal/mol from experiment.63 The barrier height at TS1 is 15.0 kcal/mol above
the ground state reactants, which is very close to the 15.4 kcal/mol activation energy reported
by Yu et al.,22 13.7 kcal/mol calculated by Walch23 with CASCCF and 14.0 kcal/mol estimated
by Green with DFT.24 All these values are, however, significantly higher than 7.4 kcal/mol
suggested by Zellner and Ewig.8 The existence of this low energy path and the possibility of
curve-crossing, as pointed out by Walch,23 may be the direct source of OH in the CH3 + O2
reaction. In the following section, we search for the location where the 2A’ and 2A” surfaces
may cross each other.
Location of Seam of Crossing: To determine the location of the seam of crossing, we
performed intrinsic reaction coordinate (IRC)65 calculations along the three minimum energy
paths, starting from TS1, TS2 and TS3, moving back toward the CH3O2 intermediates. A
similar method was employed by Yoshizawa et al.66 to study the crossing seams in the PES of the
FeO+-CH4 system. The solid, dotted and dashed lines in Fig. 3 indicate the computed potential
energy profiles along these minimum energy paths. As shown in the figure, one crossing point
MSX1 was found to locate at s = - 2.0 with the relative energy of -3.9 kcal/mol at the G2M level;
where s is the path length with an accuracy of 0.1 amu1/2 ∏bohr. Another crossing point MSX2
was found to locate at s = - 0.46 from TS3 with a relative energy of 10.6 kcal/mol at the G2M
level. The structures at these crossing points are shown in Fig. 1. The energies calculated with
the crossing-point structures with either 2A’ or 2A” symmetry agree with each other to within
0.19 kcal/mol. The fact that these crossing points lie much lower than TS1 suggests that the
chemically activated CH3O2 2A” intermediate (LM1) can decompose effectively over the 2A’
surface via TS1 to produce CH2O + OH, as first pointed out by Walch.23

3.2 Rate Constant Calculations

4
 As the population of the electronically excited state of O2 is too small to contribute even
under combustion conditions, the key mechanism for the CH3 + O2
reaction involves primarily the ground electronic state O2 (3 ∑ −g ) , producing the vibrationally
excited CH3O2 (2A”) radical, which can be stabilized by collisions, fragment to give CH3O + O
and undergo surface-crossing to the 2A’ surface to produce the CH2O + OH products via TS1.
The probability for the 2A” Ø 2A’ surface-crossing cannot be readily determined quantum-
mechanically, it was assumed to be unity in our calculation. This is probably not a poor
assumption because the crossing does not involve a spin multiplicity change and the extensive
internal and CH3 torsional excitation should help break the symmetry constraint.23 The
symmetry breaking effect of torsional motion can be qualitatively envisaged by comparing the
terminal O natural atomic orbital occupancies as a function the torsional angle of the CH3 group.
In the 2A’ state, the px, py and pz orbital occupancies are predicted to be 1.0, 1.0, and 2.0,
respectively, in both c- and t-LM2 configurations and the corresponding values in the 2A” state
are 1.1, 1.8 and 1.3 in both c- and t-LM1 configurations. The rotation of the CH3 group in the
2
A” state from the c-LM1 configuration by 20o and 40o gave rise to the predicted occupancies,
1.3, 1.6, 1.3 and 1.3, 1.6 and 1.4, respectively. These values are close to the predicted ones at the
crossing point MSX1, 1.5, 1.5 and 1.3. The large internal excitation resulting from the
association reaction is, therefore, expected to promote the 2A” → 2A’ symmetry change during
the course of the OH elimination reaction. On account of the high barrier for OH production, 45
kcal/mol (see Fig. 2), the effect of temperature on the crossing probability is expected to be
negligible.
A multi-channel variational RRKM calculation has been carried out for this reaction with the
Variflex code55 including the three major competitive product channels:
CH3 + O2 Ø CH3O2 (+M) (a)
Ø CH2O + OH (b)
Ø CH3O + O (c)
excluding the most exothermic, but kinetically noncompetitive channel forming CHO + H2O.
The energies used in the calculation are plotted in Fig. 2 and the vibrational frequencies and
moments of inertia are listed in Table 2. In the RRKM calculation, we ignore the contribution
from TS2 and TS3 since their barrier heights are 24.2 and 14.4 kcal/mol higher than that of TS1,
respectively, as mentioned in previous section. For the prediction of the quenching rates, reliable
Lennard-Jones (L-J) parameters are needed. The L-J parameters for CH3O2 (e = 303 K and s =
5.4 Å) were derived from deconvoluting the L-J potential of the He-CH3O2 system obtained by
our ab initio calculation at the MP2/6-311+G(3df, 2p) level (see Fig. 4). The ε and σ parameters
for the He-CH3O2 collision pair were determined to be 55 K and 4.0 Å by fitting the L-J
function,67 V= 4ε [(σ/r)12-(σ/r)6]. The L-J parameters of Ar and N2 were taken from the
literature.68

A. The Association Reaction CH3 + O2 Æ CH3O2

The association reaction (a) producing the methylperoxy radical dominates the CH3 + O2
process up to ~1500 K, before the fragmentation reactions (b) and (c) become competitive,
according to the early RRKM calculation of Hsu et al.14 The reaction occurs without a well-
defined transition state due to the absence of reaction barrier. To reliably predict the association
rates, the flexible variational transition state approach originally developed by Marcus and co-
workers69 has been employed by means of the Variflex code as alluded to above. The
association potential energy for the approach of CH3 and O2 forming CH3O2 (2A”) was

5
calculated by varying the forming C-O bond distance from 3.5 Å to its equilibrium value, 1.449
Å, with an interval of 0.1 Å. Other geometric parameters were fully optimized without
constraints for each C-O separation at the B3LYP/6-311G(d,p) level of theory. For each
structure, we calculated the 3N-7 vibrational frequencies, projected out of the gradient direction.
The B3LYP calculated total energy at each point along the reaction path was used to evaluate the
Varshni potential energy function60,61 given previously and then scaled to match the dissociation
energy predicted at the G2M level of theory. The values of De and b in the Varshni potential
were determined to be 33.7 kcal/mol and 1.009 Å-2, respectively. This potential was used in all
subsequent RRKM calculations.
The theoretically predicted pressure-dependent rate constants at 298 K in He are
compared with available experimental data in Fig. 5; those predicted for the association in Ar
and N2 buffer gases are compared with experimental data in Fig. 6. In the inset of Fig. 6 (a), we
also compare the predicted pressure effects on ka at different temperatures with Ar as the buffer
gas. Figure 7 compares the theoretical rate constants calculated for the high- and low-pressure
limits (in Ar) with those obtained, typically, by extrapolation of experimental data measured in
the fall-off region.
Inspection of the results presented Fig. 5 indicates that the predicted absolute rate
constants for He buffer gas with <∆E>down (average downward energy transferred per collision)
of 70 cm-1 agree quite well with the experimental data.35,38,39,40,43 Similarly for both Ar and N2
buffer gases, the experimental data28,29,35,36,44 can be very well accounted for with <∆E>down of
130 and 140 cm-1, respectively. The <∆E>down values obtained in our calculations are similar to
those evaluated by others. Keiffer et al.36 fit their experimental results (Ar gas) with the entrance
barrier constrained at 0 and 0.45 kcal/mol to get the optimal <∆E>down values of 40 cm-1 and 80
cm-1, respectively. They can also fit their experimental data with the <∆E>down of 285 cm-1. Yu et
al.22 fit their experimental data (in Ar) at the same temperature range (298-580 K) with the
<∆E>down in the range of 220~300 cm-1, assuming the entrance barrier of 0.9 kcal/mol.
From Fig. 7(a) one can see that the high-pressure limit rate constant, ka ∞ , predicted in
the present work has positive temperature dependence. At room temperature, the present
predicted rate constant is in good agreement with the values of Cobos et al.,28 Yu et al.,22 and
Laufer and Bass; 40 it is, however, higher than the extrapolated results of Pilling et al.29,36 At
higher temperatures, our value lies within those of Yu et al.,22 Forst et al.37 and Keiffer et al.36
Our low-pressure limit in Ar buffer gas, ka0, as shown in Fig.7 (b), is close agreement with the
literature data.22,28,29, 36,37

B. The CH3 + O2 Æ CH2O + OH reaction

Figure 8 compares the predicted rate constant for the production of CH2O + OH, kb, with
published data. The theoretical result computed for 1000 – 3000 K at atmospheric pressure could
be fitted to give the following expression:
kb = 1.14µ10-22T2.86 exp (-5115.4/T) cm3molecule-1 s-1
As shown in the figure, there is a large scatter in the literature data which could be classified
approximately into high1-8,31,32,33 and low value groups.9-22 The high-value group contains those
results obtained with channel (b) assumed to be the dominant one; the kinetics of the overall
CH3 + O2 reaction were mostly determined without the benefit of ARAS or LRAS for O or OH
concentration measurements. On the other hand, the low-value group consists of those studies
which employed either ARAS for O detection or LRAS for OH measurement. The predicted rate
constant agrees better with the more recent measurements with ARAS and/or LRAS diagnostics.

6
C. The CH3 + O2 Æ CH3O + O reaction
The decomposition of CH3O2 to CH3O + O, similar to its formation by the entrance
channel, does not have a well-defined transition state. The variational treatment was employed to
obtain the dissociation potential energy function by varying the breaking O-O bond from 2.2 to
3.2 Å at an interval of 0.1 Å. The computed potential energies could be fitted to the Varshni
function with the parameter of b =0.637 Å-2. The value of De was obtained by using the heat
formation of CH3O predicted by a series of isodesmic calculations because of the under
prediction of the endothermicity for the CH3 + O2 Ø CH3O + O overall reaction as previously
mentioned. As shown in Table 4, the average heat formation of CH3O, calculated with 5 different
isodesmic reactions is 5.4 ≤ 0.5 kcal/mol, agrees very well with most recent experimental values,
5.47 ≤ 0.770, 5.6 ≤ 0.271 and 5.9 ≤ 0.9 kcal/mol,72 except that of Neumark and co-workers, 6.8 ≤
0.4 kcal/mol determined by the photo-fragmentation dynamics of CH3OH.73 For our multi-
channel RRKM calculations of the rate constant, the dissociation energy of 59.2 kcal/mol based
on the isodemic result was used.
The predicted rate constant is compared with existing experimental data in Fig.9. The
least-squares fitted theoretical expression, kc =1.01µ10-16T1.54exp(-13275.7/T) cm3 molecule-1s-1
covering the temperature range 1000-3000 K under atmospheric conditions, agrees closely with
the results of Bhaskaran et al.,11 Klatt et al.15 Yu et al.,22 and Braun-Unkhoff and coworkers,17
but somewhat higher than the most recent works of Michael et al.20 and Hwang and coworkers.21

D. Product branching ratios

RRKM calculations can provide the individual rate constants for any practical conditions
of interest to combustion. In Table 5, we present the values for the high pressure limit (k ∞ ) and
the total rate constants (ktot) as well as the product branching ratios calculated for the
atmospheric pressure. These data are also graphically presented in Fig. 10. As can be more
readily seen from the figure that under atmospheric pressure conditions, the formation of CH3O2
by collisional stabilization dominates the reaction up to about 1250 K, at which the CH2O + OH
product formation becomes competitive. The production of CH3O + O, contrary to recent
assumption,20,21 appears to be a minor process below 2000 K.

4. Concluding Remarks
The detailed potential energy surfaces computed at the G2M level and the rate constants
predicted with the Variflex code of Klippenstein et al. for three product channels of the CH3 +
O2 reaction have been presented. The predicted rate constants for the formation of three major
products, CH3O2, CH2O + OH and CH3O + O, agree well with published experimental data.
Under atmospheric pressure conditions, the formation of the collisionally stabilized CH3O2 was
found to dominate up to ~ 1200 K, above which the formation of the CH2 + OH products become
competitive. The CH2O + OH products were formed by the crossing of the excited CH3O2 from
the 2A” to the 2A’surface, followed by fragmentation with a barrier of 15 kcal/mol above the
reactants. Significantly, the most exothemic product channel producing HCO + H2O was found
kinetically unimportant due to its very high barrier.
The predicted relative energies for the CH3OO intermediate and the products, CH2O+
OH and CH3O + O, agree with experimental values within ≤ 1 kcal/mol, typical for the G2M
method for the present size systems.52 We have tested the effect of the possible error in energy
on the predicted rate constants for the two product channels by raising the energy at TS1 and the

7
enthalpy change associated with the variational TS producing CH3O + O each by 1 kcal/mol. The
predicted rate constant for CH2O + OH formation decreases by 7.6% at 1500 – 3000 K,
independent of temperature, whereas, the corresponding changes in the rate constant for CH3O +
O production are 25% at 1500 K and 6.5% at 3000 K. The result of this brief test suggests that
our theoretical rate constants for the formation of these products are reliable within ≤ 25%, as
has been supported by the reasonable agreement with recent experimental data.
Mechanistically, the reaction of CH3 with O2 differs significantly from its analogous
processes involving larger alkyl radicals, which contain one or more β -CH bonds. For example,
C2H5 + O2; it can undergo facile isomerization and disproportionation reactions producing C2H4
+ HO2. A similar process in CH3 + O2 producing CH2 + HO2 is highly endothermic. A detailed
mechanism for the C2H5 + O2 reaction has been presented recently by Rienstra-Kiracofe et al.76
It should also be mentioned that the present system differs noticeably from the analogous
SiH3 + O2 reaction in several respects.77,78 First of all, the formation of H2SiOOH following the
exothermic association/isomerization reaction is non-thermally activated. The chemically
activated H2SiOOH can undergo several isomerization/ fragmentation reactions producing
H2SiO + OH, HSiOH + OH, Si(OH)2 + H, and SiO + H2 + H exothermically. Secondly, the
production of H3SiO + O is endothermic by about 11 kcal/mol;77 it cannot compete effectively
with all the aforementioned exothermic product channels.

Acknowledgments
This work is sponsored partially by the Basic Energy Science, Department of Energy
under grant No. DE-FG02-97-ER14784 (to RZ) and partially by the Caltech Multidisciplinary
University Research Initiative under ONR grant No. N00014-95-1-1388 (to CCH and MCL).

References
[1] A. M. Dean, G. B. Kistiakowsky, J. Chem. Phys. 54, 1718 (1971).
[2] T. P. Izod, G. B. Kistiakowsky, S. Matsuda, J. Chem. Phys. 55, 4425 (1971).
[3] C. Jachimowski, J. Combust. Flame 23, 233 (1974).
[4] T. Tsuboi, Jpn. J. Appl. Phys. 15, 159 (1976).
[5] D. B. Olson, W. C. Gardiner, Jr. Combust. Flame, 32, 151 (1978).
[6] K. Tabayashi, S. H. Bauer, Combust. Flame, 34, 63 (1979).
[7] K. Saito, R. Ito, T. Kakumoto, A. Imamura, J. Phys. Chem. 90, 1422 (1986).
[8] R. Zellner, F. Ewig, J. Phys. Chem. 92, 2971 (1988).
[9] C. T. Bowman, Fifteenth Symposium (International) on Combustion; The
Combustion Institute: Pittsburgh, PA, 1975; p 869.
[10] A. C. Baldwin, D. M. Golden, Chem. Phys. Lett. 55, 350 (1978).
[11] K. A. Bhaskaran, P. Frank, Shock Tubes and Shock Waves, Proceedings
of the Twelfth International Symposium on Shock Waves; A. Lifshitz, R. Rom,
Eds.; Magnes Press: Jerusalem, 1980; p 503.
[12] M .A. Teitelboim, V. I. Vedeneev, N. Y. Goldenberg, A. A. Karnaukh, Eleventh
International Symposium on Gas Kinetics; Assissi, Italy, 1990.
[13] C. H. Wu, C. –Y. Lin, H. –T. Wang, M. C. Lin, In Current Topics in Shock Waves; Kim,
Y. W., Ed.; Seventeenth International Symposium on Shock Waves and Shock Tubes, AIP
Conference Proceedings 208; American Institute of Physics: New York, 1990; p 450.
[14] D. S. Y. Hsu, W. M. Shaub, T. Creamer, D. Gutman, M. C. Lin, Ber. Bunsen-
Ges. Phys. Chem. 87, 909 (1983).

8
[15] M. Klatt, M. Röhrig, H. Gg. Wagner, Ber. Bunsen-Ges. Phys. Chem. 95, 1163
(1991).
[16] M. A. Grela, V. T. Amorebieta, A. J. Colussi, J. Phys. Chem. 96, 7013 (1992).
[17] M. Braun-Unkhoff, C. Naumann, P. Frank, In Shock Waves; Brun, Raymond,
Cumitrescu, Lucien, Eds.; Nineteenth International Symposium on Shock Waves;
Springer: Berlin, Germany, 2, 203 (1995).
[18] T. A. Brabbs, R . S. Brokaw, Fifteenth Symposium (International) on Combustion;
The Combustion Institute: Pittsburgh, PA, 1975; p 147.
[19] A. M. Dean, P. R. Westmoreland, Int. J. Chem. Kinet. 19, 207 (1987).
[20] J. V. Michael, S. S. Kumaran, and M. C. Su., J. Phys. Chem. A 103, 5942 (1999).
[21] S. M. Hwang, Si-Ok Ryu, and K. J. De. Witt, M. J. Rabinowitz, J. Phys. Chem. A, 103,
5949 (1999).
[22] C. L. Yu, C. Wang, and M. Frenklach, J. Phys. Chem. 99, 14377 (1995).
[23] S. P. Walch, Chem. Phys. Lett. 215, 81 (1993).
[24] W. H. Green, Int. J. Quantum Chem. 52, 837 (1994).
[25] E. Sicilia, F. P. DiMaio, N. Russo,. Chem. Phys. Lett. 225, 208 (1994).
[26] D. Seery, J. Symp. Int. Combust. Proc. 12, 588 (1969).
[27] F. B. Marcotte, W. A. Jr. Noyes, Discuss. Faraday Soc. 10, 236 (1951).
[28] C. J. Cobos, H. Hippler, K. Luther, A. R. Ravishankara, J. Troe, J. Phys. Chem.
89, 4332 (1985).
[29] M. J. Pilling, M. J. C. Smith, J. Phys. Chem. 89, 4713 (1985).
[30] M. A. Teitelboim, L. B. Romanovich, B. I. Vedeneev, . Kinet. Katal. 19, 399
(1978).
[31] D. F. Cooke, A. Williams, A. Symp. Int. Combust. Proc. 13, 757 (1971).
[32] D. L. Baulch, C. J. Cobos, R. A. Cox, C. Esser, P. Frank, Th. Just, J. A. Kerr, M. J.
Pilling, J. Troe, R. W. Walker, J. Warnatz, J. Phys. Chem. Ref. Data, 21, 411 (1992).
[33] A. A. Borisov, E. V. Dragalova, V. M. Zamanskii, V. V. Lisyanskii, G. I. Skachkov, Kinet.
Catal. 22, 305 (1981).
[34] J. Warnatz, Combustion Chemistry (ed. W. C. Gardiner, Jr.) Springer-Verlag, NY1984,
197.
[35] E. A. Selzer, K. D. Bayes, J. Phys. Chem. 87, 392 (1983).
[36] M. Keiffer, M. J. Pilling, M. J. C. Smith, Phys. Chem. 91, 6028 (1987).
[37] W. Forst, F. Caralp, J. Chem. Soc. Faraday Trans., 87, 2307 (1991).
[38] J. Washida, Chem. Phys. 73, 1665 (1980).
[39] I. C. Plumb, K. R. Ryan, Int. J. Chem. Kinetics, 14, 861 (1982).
[40] A. H. Laufer, A. M. Bass, Int. J. Chem. Kinetics, 7, 639 (1975).
[41] C. J. Hochanadel, J. A. Ghormley, J. W. Boyle, P. J. Ogren, J. Phys. Chem. 81, 3
(1977)
[42] D. A. Parkes, Int. J. Chem. Kinet. 9, 451 (1977).
[44] N. Basco, D. G. L. James, F. C. James, Int. J. Chem. Kinetics. 4, 129 (1972).
[43] E. W. Kaiser J. Phys. Chem. 97, 11681 (1993).
[45] T. H. Dunning, Jr and P. J. Hay, in: Methods of electronic structure theory, ed. H. F.
Schaefer III (Plenum Press, New York, 1977).
[46] N. Godbout, J. Andzelm, E. Wimmer,. and D. R. Salahub, Can. J. Chem. 70, 560 (1992).
[47] J. Andzelm, E. Radzio, and D. R. Salahub, J. Comput. Chem. 6, 520 (1985).
[48] A. D. Becke, J. Chem. Phys.98, 5648 (1993).

9
[49] A. D. Becke, J. Chem. Phys. 96, 2155 (1992).
[50] A. D. Becke, J. Chem. Phys. 97, 9173 (1992).
[51] C. Lee, W. Yang, R. G. Parr, Phys. Rev. 37B, 785 (1988).
[52] A. M. Mebel, K. Morokuma, M. C. Lin, J. Chem. Phys. 103, 7414 (1995).
[53] M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M . W. Gill, B. G. Johnson, M. A. Robb, J. R.
Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V.
G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M.
Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R.
Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-
Gordon, C. Gonzalez and J. A. Pople, GAUSSIAN 98, REVISION A.1; Gaussian, Inc., Pittsburgh
PA, 1998.
[54] MOLPRO is a package of ab initio programs written by H.-J. Werner and P. J. Knowles,
with contributions from J. Almlöf, R. D. Amos, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J.
Dobbyn, F. Eckert, S. T. Elbert, C. Hampel, R. Lindh, A. W. Lloyd, W. Meyer, A. Nicklass, K.
Peterson, R. Pitzer, A. J. Stone, P. R. Taylor, M. E. Mura, P. Pulay, M. Schütz, H. Stoll and T.
Thorsteinsson.
[55] S. J. Klippenstein, A. F. Wagner, R. C. Dunbar, D. M. Wardlaw, and S. H. Robertson,
VARIFLEX: VERSION 1.00, 1999.
[56] R. G. Gilbert, S. C. Smith, Theory of Unimolecular and Recombination Reactions,
Blackwell Scientific, Carlton, Australia, 1990.
[57] K. A. Holbrook, M. J. Pilling, and S. H. Robertson, Unimolecular Reactions,
Wiley, 1996.
[58] J. Troe, J. Chem. Phys. 66, 6745 (1977).
[59] R. S. Zhu, M. C. Lin, J. Phys. Chem. A, 104 10807 (2000).
[60] V. P. Varshni, Rev. Mod. Phys. 29, 664 (1957).
[61] S. J. Klippenstein, L. R. Kundhar, A. H. Zewail, R. A. Marcus, J. Chem. Phys. 89,
4761 (1988).
[62] I. R. Slagle and D. Gutman, J. Am. Chem. Soc., 107, 5432 (1985).
[63] Jr. M. W. Chase, C. A. Davies, Jr. J. R. Downey, D. J. Frurip, A. A. McDonald, and A. N.
Syverud, J. Phys. Chem. Ref. Data, 14, Suppl. 1 (1985).
[64] B. Rosen, ed., Spectroscopic data relative to diatomic molecules (Pergamon Press, Oxford,
1970)
[65] C. Gonzalez, H. B. Schlegel, J. Phys. Chem.90, 2154 (1989).
[66] K. Yoshizawa, Y. Shiota, T. Yamabe, J. Chem. Phys. 111, 538 (1999).
[67] J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular theory of gases and
liquids. 2nd ed. John Wiley and Sons Inc., New York, NY., 1964.
[68] H. Hippler, J. Troe, and H. J. Wendelken, J. Chem. Phys. 78, 6709 (1983).
[69] D. M. Wardlaw and R. A. Marcus, Chem. Phys. Lett. 110, 230 (1984); J. Chem.
Phys. 83, 3462 (1985); S. J. Klippenstein, J. Chem. Phys. 96, 367 (1992); S. J.
Klippenstein and R. A. Marcus, J. Chem. Phys. 87, 3410 (1987).
[70] O. A. Mazyar, T. Baer, J. Phys. Chem. A, 103, 1221 (1999).

[71] J. L. Holmes, F. P. Lossing, Int. J. Mass Spectrom. Ion Processes, 58, 113 (1984).

[72] Handbook of Chemistry and Physics, D. R. Lide, editor-in-chief, 78th edition, p. 9-

71, CRC, Press, 1997-1998, Boca Raton, Florida.

10
[73] D. L. Osborn, D. J. Leahy, E. M. Ross, D. M. Neumark, Chem. Phys. Lett.,
235, 484 (1995).
[74] M. W. Chase, Jr. NIST-JANAF Thermochemical Tables, Fourth Edition, Woodbury, New
York, 1998.
[75] C. W. Jr. Bauschlicher, H. Partidge, Chem. Phys. Lett. 208, 241 (1993).
[76] J. C. Rienstra-Kiracofe, W. D. Allen and H. F. Schaefer, III. J. Phys. Chem. A. 104, 9823
(2000).
[77] C. L. Darling and H. B. Schlegel, J. Phys. Chem. 98, 8910 (1994).
[78] Y. Murakami, M. Koshi, H. Matsui, K. Kamiya and H. Umeyama, J. Phys. Chem. 100,
17501 (1996).

11
Table 1. Total and Relative Energies of Reactants, Intermediates, Transition
States and Products for the Reaction of CH3 with O2 Calculated at
Different Levels of Theory with B3LYP/6-311G(d, p) Optimized
Geometries.

Energiesb

Species ZPEa B3LYP/ MP2/ MP2/ CCSD(T)/ G2M

6-311G (d, p) 6-311G(d, p) 6-311+G(3df, 2p) 6-311G (d, p)
CH3 + O2(3 Σ −g ) 20.9 -190.218548 -189.7307117 -189.8393013 -189.769878 -189.8783

CH3 + O2(1 ∆ g ) 20.9 39.0 31.9 30.1 30.6 26.3

CH2O+OH 21.9 -45.4 -48.4 -52.9 -50.0 -53.5

CH3O+O 22.7 29.5 32.7 35.8 23.5 27.7
HCO+H2O 21.5 -72.5 -79.5 -87.7 -76.4 -83.9
t-LM1c, Cs, 2A'' 26.9 -33.4 -24.0 -29.7 -30.6 -30.4
c-LM1c, Cs, 2A'' 26.6 -32.6 -23.1 -28.9 -29.4 -29.6
t-LM2 c, Cs, 2A' 26.6 -11.6 -3.7 -8.9 -9.7 -9.2
c-LM2 c, Cs, 2A' 26.2 -8.2 -0.1 -5.6 -6.2 -6.4
LM3, C1 25.2 -16.7 -13.2 -20.9 -15.0 -18.5
2
TS1, Cs, A' 22.4 17.7 35.9 28.8 20.7 15.0
TS2, Cs, A'' 24.3 36.3 56.4 49.3 43.0 39.2
TS3, C1 23.0 30.5 35.9 27.6 35.5 29.4
TS4, C1 24.2 -13.2 17.3 11.3 -8.6 -11.3
TS5, C1 21.6 49.5 60.9 53.4 54.2 47.4
MSX1 23.4 11.6 30.2 24.4 13.8 10.6
MSX2 25.6 -5.5 4.4 -1.5 -2.7 -3.9

a
Values are in units of kcal/mol
b
The total energies are in units of a.u and the relative energies are in units of kcal/mol.
c
c-LM1 , t-LM1 and c-LM2, t-LM2 are defined as those in Fig. 1

12
Table 2. Vibrational Frequencies and Moments of Inertia for Reactants,
Intermediates, Transition States and Products of the CH3 + O2
Reaction at B3LYP/6-311G(d, p) Level of Theory.a

Species Ii (au) Frequencies

CH3 6.3, 6.3, 12.6 504, 1403, 1403, 3105, 3284, 3284
O2(3 Σ −g ) 41.5, 41.5 1638

O2(1∆g) 41.5, 41.5 1628

CH2O 6.3, 46.2, 52.6
OH 3.2, 3.2
c-LM1 33.5,162.4,184.3
t-LM1 34.2, 160.0, 182.7
c-LM2 37.1, 163.2, 188.6
t-LM2 37.4, 159.6, 185.4
LM3 33.9, 161.9, 187.8
TS1 51.5, 126.3, 165.1
TS2 34.6, 158.0, 181.3
TS3 41.1, 131.3, 164.9
TS4 33.9, 175.2, 206.5
TS5b 39.9, 141.3, 172.7
MSX1 47.6, 129.9, 165.9
MSX2 38.1,146.2, 172.8
1202, 1270, 1539, 1827, 2868, 2917
3704
-137i,527, 907, 1113, 1131,1234, 1432, 1472, 1481, 3044, 3129, 3162
135, 294, 914, 1129, 1156, 1218, 1446, 1469, 1484, 3049, 3140, 3156
-280 i, 367, 908, 1008,1146,1177,1457,1475,1493, 3035, 3115,3134
256, 371, 916, 1028, 1169, 1176, 1453, 1459, 1510, 3018, 3086, 3147
156, 237, 480, 653, 841, 1134, 1192, 1363,1432, 3115, 3259, 3744
1882i, 202, 751, 762, 1013, 1078, 1109, 1165, 1474, 1950, 3048, 3164
-555 i, 518, 749, 907, 924, 958, 1223, 1369, 1391, 2945, 2983, 2996
-2566, 572, 635, 848, 999,1099, 1160, 1290, 1549, 1884, 2959, 3104
-1373 i, 188, 409, 502, 826, 1123, 1148, 1260, 1449, 3053, 3198, 3783
-3176 i, 431, 707, 797, 963, 1118, 1148, 1399, 1899, 2575, 3102, 3697
364 i, 706, 903, 1094, 1145, 1187, 1463,1507,1512, 3016, 3160, 3231
403, 730, 869, 1101,1135,1157, 1328,1416,1484, 2159, 3046, 3097

a.The geometries of various species are given in Fig. 1.

b. This transition state was located at the MP2/6-311(d, p) level since we failed to locate it by
B3LYP/6-311G(d, p).

13
Table 3. Calculated High Pressure and Low Pressure Limiting Rate Constants for
Association Reaction of CH3+O2→CH3O2 in Ar at some
Selected Temperatures.

T ( K) k∞ k0
(cm3molecule-1s-1) (cm6molecule-2s-1)
298 1.80×10-12 2.52×10-30
334 2.17×10-12 1.49×10-30
382 2.71×10-12 7.87×10-31
420 3.16×10-12 4.96×10-31
474 3.85×10-12 2.68×10-31
530 4.61×10-12 1.49×10-31
583 5.37×10-12 8.9×10-31

Table 4. The Heat Formation of CH3O Calculated by the Isodemic Method

at the G2M level. Values are in units of kcal/mola.

Reaction DrH0 (0K) DfH0 (CH3O, 0K)

CH3 + NO2 Ø CH3O + NO -17.36 5.37≤0.3
CH3 + OH Ø CH3O + H 12.30 5.50≤0.5
CH3 + O2H Ø CH3O + OH -24.86 5.36≤1.1
CH4 + OH Ø CH3O + H2 12.29 5.48≤0.4
CH3 + H2OØ CH3O + H2 26.64 5.10≤0.2

Average 5.36≤0.5

Exp 5.47≤0.7 70
5.6≤0.2 71
5.9≤0.9 72
6.8±0.4 73
a
The species heats of formation at 0 K, were taken from Ref. 74, except that of HO2
from Ref. 75. The errors given in the calculated values convolute all reported
experimental ones.

14
Table 5. Theoretically Predicted Branching Ratios and ktot. at 1 atm. and
High Pressure in Ar in units of cm3 molecule-1 s-1

T(K) ka/ ktot kb/ ktot kc/ ktot ktot kinf

500 1.00 0.00 0.00 2.99×10-13 4.37×10-12
800 1.00 0.00 0.00 4.00×10-14 9.16×10-12
1000 0.97 0.03 0.00 9.86×10-15 1.28×10-11
1110 0.86 0.13 0.01 4.41×10-15 1.50×10-11
1200 0.59 0.38 0.03 2.69×10-15 1.68×10-11
1300 0.21 0.70 0.09 2.57×10-15 1.88×10-11
1400 0.05 0.80 0.15 3.67×10-15 2.09×10-11
1500 0.01 0.79 0.20 5.79×10-15 2.31×10-11
1800 0.00 0.67 0.33 2.05×10-14 2.97×10-11
2000 0.00 0.59 0.41 4.14×10-14 3.43×10-11
2500 0.00 0.47 0.53 1.67×10-13 4.62×10-11
3000 0.00 0.39 0.61 4.69×10-13 5.83×10-11

15
Figures captions

Fig.1 The optimized geometries of the reactants, intermediates, transition states and

products (except O2, H2O, and CH2O) computed at the B3LYP/6-311G(d, p)

level.

Fig. 2 Schematic energy diagram of the CH3-O2 system computed at the G2M level.

Fig. 3 Potential energies along those IRC paths from TS1, TS2, TS3 to intermediates for

s<0 (s is the length of IRC).

Fig. 4 The L-J potential of the He-CH3O2 system computed at the MP/6-311+G(3df,

2p) level, solid circles are the calculated data, solid curve is the fitting result.

Fig. 5 Comparison of the predicted rate constants (curves) with experimental literature

data (symbols) in bath gas He for CH3 + O2 Ø CH3O2.

Fig. 6 Comparison of the predicted rate constants (curves) with experimental literature

data (symbols) in bath gases Ar and N2 for CH3 + O2Ø CH3O2.

Fig. 7 Comparison of the experimental and calculated rate constants for high-pressure

(a) and low-pressure (b) limits in Ar bath gas.

Fig.8 Comparison of the predicted and experimental rate constants for

CH3 + O2 ØCH2O + OH. References are given as labeled.

Fig.9 Comparison of the predicted and experimental rate constants for

CH3 + O2 Ø CH3O + O. References are given as labeled.

Fig.10 Predicted rate constants, plotted in the Arrhenius form, for the three product

channels as well as the total rate constant at 1 atm. and the high-pressure limit.

16
 H H
1 O
120.0 H H 1.088 H

108.3 O
H
112.4 113.3 1.317
1.317
1.091 1.453 O O

1.080 H 109.9 1.449

H

c-LM1, Cs,2A"
H
1
CH3, D3h, 2A" t-LM1, Cs, 2A"
(O-O-C-H1=0.0) (O-O-C-H1=180.0)
O H
H 1 H 1.358 O

1.089 1.094 107.8 1.083 1.456

H
H
1.386 109.1
110.4 O 1.435 100.4
108.0 O O
1.389 1.089 104.2 1.094 H

1.092 1.448 O H 0.969

1 H
H
c-LM2, Cs,2A' t-LM2, Cs, 2A' LM3
(O-O-C-H1=0.0) (O-O-C-H1=180.0)

1 H
1.012 H
1.341
1.268 O 1.968 O
1 H
95.1 O
1.389 99.8
101.8 83.3 H
126.1 H

1.336 1.509 108.3 1.413 77.9 1.394

O
H
88.7 O
O
1.397 1.384
1.379 H
H
115.4 1
H

TS1, Cs, 2A' TS2, Cs, 2A" TS3, C1

H
H
H 1.504 1.098
O
1.221
1.087 1.300 O
105.0 77.4
1.177 H
81.6
107.3 1.626 80.8 108.9 102.9 1.327
O
96.8 1.325 H
1.090 117.4 95.3 H O 1.473 O

H H 1.523 H
O
0.968 TS5, C1 MSX1
TS4, C1
H

H O
1.109
1.216 1.174 105.3
1.127 O
H
97.6 1.379
O 124.0 H
1.365
O H
1.397
H
H
MSX2 HCO, Cs, A' 2
CH3O, Cs, 2A'

Fig. 1 Zhu, J. Chem. Phys.

17
 Kcal/mol

TS5,2A
47.4
50.0
TS2, 2A"
40.0 39.2
CH3+1O2 TS3,2A
30.0 26.3 29.4 CH3O+O
27.7
20.0 MSX2

10.0 TS1
3 2
CH3+ O2 MSX1 A'
0.0 15.0
2 TS4,2A
-10.0 c-LM2, A' -11.3
-6.4
-20.0
LM3,2A
-30.0 -18.5
c-LM1, 2A" t-LM1, 2A"
-40.0 -29.6 -30.4 CH2O+OH
-50.0 -53.5

-60.0

-70.0
HCO+H2O
-80.0 -83.9

-90.0

Fig. 2 Zhu, J. Chem. Phys.

18
 2
-190.16 TS2 A"
Total Energy (Hartree)

2
TS3( A)
-190.18 2
TS1( A')
-190.20 MSX2

-190.22 MSX1
2
LM2( A')
-190.24

2
-190.26 c-LM1( A") (see Fig.1)
2
-190.28 t-LM1( A")(see Fig.1)

-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
1/2
-s(amu bohr)

Fig. 3 Zhu, J. Chem. Phys.

19
 120
Calculated data
80 solid line is the fitting result
V(R)/K

40

-40

-80

3 4 5 6 7 8
o
Interaction Coordinate A

Fig. 4 Zhu, J. Chem. Phys.

20
 10
-1
cm molecule s

CThis work
-1

35
ESelzer et al.
38
HWashida
40
JLaufer et al.
1 43
NKaiser
3

39
He 298 K PPlumb et al.
-13
ka /10

0.1

-1 0 1 2 3 4 5 6
10 10 10 10 10 10 10 10
He Pressure (Torr)

Fig.5 Zhu, J. Chem. Phys.

21
 29
(cm molecule s )
exp. Pilling and Smith
-1 -1

28
exp. Cobos et al.
10
35
exp. Selzer et al. (a)
8

"Data from Ref. 36"

-1
cm molecule s
6 334 K
1

-1
3

4 420 K

3
2 530 K

-13
k/10
0.1
-13

0
ka/10

0 100 200 300 400 500

Pressure (Torr)

0.01
-1 0 1 2 3 4 5 6
10 10 10 10 10 10 10 10
Ar Pressure (Torr)

(b)

10
-1
cm molecule s
-1

This w ork
28
1 Cobos et al.
44
3

Basco et al.
35
Selzer et al.
-13

43
Kaiser
k/10

0.1
-1 0 1 2 3 4 5 6
10 10 10 10 10 10 10 10
N 2 Pressure (Torr)

Fig.6 Zhu, J. Chem. Phys.

22
 Current work
22 (a)
Yu et al.
28
cm molecule s )
Cobos et al.
-1

8 32
Baulch et al.
-1

7 Keiffer et al.
36

29
6 Pilling and Smith et al.
43
Kaiser et al.
5 R Laufer et al.
40

41
4 S Hochanadel, et al.
3

42
TParkes et al.
3
-13

2
ka /10

1
∞

1.5 2.0 2.5 3.0 3.5

1000/T

22
Y u et al.
28
C obo s et al.
29
(b)
P illing et al.
36
K eiffer et al.
-2 -1

-30 37
ka cm molecule s

10 Forst et al.

-31
10
6
0

-32
10

1.5 2.0 2.5 3.0 3.5

1 00 0 /T K

Fig. 7 Zhu, J. Chem. Phys.

23
 -10
10

-11
10 1
k (cm molecule s )
-1 -1

-12
10 6
5
-13
10 2 32 33
8
-14
10 7
9
3

31
-15 11 This work
10 17
22
-16
10
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

1000/T (K)

Fig.8 Zhu, J. Chem. Phys.

24
 -12
10

-13
10
7
k (cm molecule s )

22
-1 -1

-14
10 11

-15 18
10 20
15 14
8
3

-16 17
10 21
This work
-17 34
10
13

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

1000/T (K)

Fig.9 Zhu, J. Chem. Phys.

25
 -10
10
∞
k
-12
10
-1 -1

ktot
k cm molecule s

-14
1 atm
10

-16
10
3

CH2O+OH (kb)

-18
10
CH3OO (ka) CH3O+O (kc)
-20
10
0.4 0.8 1.2 1.6 2.0
1000/T (K)

Fig.10 Zhu, J. Chem. Phys.

26