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pubs.acs.org/JPCA
Department of Aerospace and Mechanical Engineering, University of Southern California, Los Angeles, California 90089-1453,
United States
National Institute of Standards and Technologies, Gaithersburg, Maryland 20899, United States
bS Supporting Information
ABSTRACT: The role of quantum tunneling in hydrogen shift in
linear heptyl radicals is explored using multidimensional, smallcurvature tunneling method for the transmission coecients and a
potential energy surface computed at the CBS-QB3 level of theory.
Several one-dimensional approximations (Wigner, Skodje and
Truhlar, and Eckart methods) were compared to the multidimensional results. The Eckart method was found to be suciently
accurate in comparison to the small-curvature tunneling results for
a wide range of temperature, but this agreement is in fact fortuitous
and caused by error cancellations. High-pressure limit rate constants were calculated using the transition state theory with treatment of hindered rotations and Eckart transmission coecients for all
hydrogen-transfer isomerizations in n-pentyl to n-octyl radicals. Rate constants are found in good agreement with experimental kinetic data
available for n-pentyl and n-hexyl radicals. In the case of n-heptyl and n-octyl, our calculated rates agree well with limited experimentally
derived data. Several conclusions made in the experimental studies of Tsang et al. (Tsang, W.; McGivern, W. S.; Manion, J. A. Proc.
Combust. Inst. 2009, 32, 131138) are conrmed theoretically: older low-temperature experimental data, characterized by small preexponential factors and activation energies, can be reconciled with high-temperature data by taking into account tunneling; at low
temperatures, transmission coecients are substantially larger for H-atom transfers through a ve-membered ring transition state than
those with six-membered rings; channels with transition ring structures involving greater than 8 atoms can be neglected because of entropic
eects that inhibit such transitions. The set of computational kinetic rates were used to derive a general rate rule that explicitly accounts for
tunneling. The rate rule is shown to reproduce closely the theoretical rate constants.
1. INTRODUCTION
Understanding the thermal decomposition reactions of alkyl
radicals is critical to the development of combustion models of
hydrocarbon fuels. In n-alkane oxidation at high temperatures,
alkyl radicals are initially formed by CC or CH ssion in the
fuel molecule or H-abstraction reaction by a free radical. Small
alkyl radicals (Ce3) decompose mainly by CC -scission, as
the 12 and 13 hydrogen shifts can occur only through threeor four-membered ring transition state structures with large
energy barriers due to strain energies.1 For large alkyl radicals,
the thermal decomposition is complicated by internal hydrogen shifts.27 These isomerization processes occur through
cyclic transition state structures. Internal isomerization can occur
through ve-, six-, or seven-member ring transition state structures, which may be denoted as 14, 15, and 16 hydrogen
shifts, respectively. Some of these transition state structures are
associated with ring strain energies, while others are practically
unstrained. H-atom shifts are the predominant unimolecular
reactions under lower temperature conditions. As the temperature is increased, -scissions become increasingly important,
but H-atom shift remains critical to the dissociation of alkyl
radicals and especially the product distributions resulting from
the -scission processes. The combustion chemistry of olens
r 2011 American Chemical Society
ARTICLE
Figure 1. Arrhenius plots of (a) 14 hydrogen shift in n-pentyl radical, and (b) 15 hydrogen shift in n-hexyl radical.
Reactions involving the transfer of a hydrogen atom are inherently subject to quantum tunneling eect.13 The role of tunneling in n-alkyl radical isomerizations was recently highlighted by
Tsang and co-workers.47 They showed that tunneling must be
considered to reconcile older data obtained at low temperatures
with measurements made in their high-temperature single-pulse
shock tube. Low-temperature kinetic data have been subject to
controversies because of the unusually small pre-exponential factors
(A) that were dicult to rationalize with the thermochemical
kinetic theory.14 Direct measurements of the isomerization reaction
rates of alkyl radicals are dicult, and kinetic data were derived
usually from analyses of complex reaction mechanisms. Moreover,
most experiments were performed in the fallo region and/or
involved a chemically activated process. In such cases, the highpressure limit rate constant must be extrapolated from the Rice
RamspergerKasselMarcus (RRKM) theory and, for the latest
studies, from Master Equation (ME) analysis.
Among all n-alkyl radicals, the unimolecular reactions of
1-pentyl and 1-hexyl have been studied most extensively in the
past. Figure 1 presents selected literature rate constants. Endrenyi and Le Roy15 proposed the rst experimental rate constant
for the gas-phase 14 hydrogen migration in n-pentyl radicals:
1 C5 H11 / 2 C5 H11
R1
Using the same experimental approach, these authors also proposed rate expressions for n-octyl radicals isomerization with
similar A factors. Marshall22 examined the thermal decomposition
of n-pentane in the temperature range of 737923 K and pressures below 200 Torr. The rate expression for the 14 hydrogen
shift of reaction R1 was derived from the distribution of major
products as
R2
They reported:
k1 s1 1:4 107 e5440=T
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and proposed:
k2 s1 3:16 1010 e8560=T
and
k2, s1 6:7 107 T 0:823 e6570=T
10
11
12
13
14
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(ZPE) were quite close at the B3LYP/6-311G(2d,d,p) and CBSQB3 levels of theory (Table 1).
Hindered Internal Rotations. The description of isomerization channels of large aliphatic chains requires an accurate treatment of low-frequency internal rotations. Using the harmonic
oscillator (HO) approximation to describe these torsion modes
can lead to large errors in the partition function. Vansteenkiste
et al.38 calculated the thermodynamic properties of n-alkanes
using a quantum-mechanical treatment and showed that treating
hindered internal rotation is critical to obtain accurate entropies
and heat capacities values. As hydrogen transfers occur through
cyclic transition state structures, most of the internal rotations of
the initial reacting radicals are locked in the ring, and the rate
coefficients will be strongly dependent on the entropy variation.
As an example, Vansteenkiste et al. reported for n-heptane a
difference of 9.3 cal/(mol K) at 1000 K in entropy between
calculations using the assumption of harmonic oscillator (HO)
and a more precise quantum mechanical treatment. The HO
approximation underestimates the entropy change. In the present work, hindered internal rotations were treated using the
following procedure. First, the potentials of each internal rotation
of 1-pentyl, 2-pentyl, and 3-pentyl radicals were calculated at the
B3LYP/6-311G(2d,d,p) level of theory using a relaxed energy
scan. The energy barriers for these hindered internal rotors were
then calculated at the CBS-QB3 level of theory. The characteristics of the rotational potentials and the barriers of rotation
obtained were used to correct the HO partition function using
Pitzer and Gwinn tabulations.39 Rotational potential functions and
barriers for each internal rotor in n-pentyl were used for similar
internal rotors found in largest alkyl radicals. Reduced moments of
inertia for internal rotations were calculated for each species using
B3LYP/6-311G(2d,d,p) geometries with the method of Pitzer
implemented in ChemRate.40,41 For cyclic transition states, the
vibrational modes of the cyclic part of the molecular structure were
described within the HO approximation, and the lateral alkyl
group internal rotations were treated as hindered rotors (HR) via
relaxed scans (with cyclic bond lengths frozen) in the critical geometries for 1-pentyl to 2-pentyl and 1-hexyl to 3-hexyl. Parameters
for HR corrections for these two critical geometries were used for
all other similar internal rotors found in the saddle point geometries of larger alkyl radicals. Hindrance potentials and barrier
heights are given in the Supporting Information.
Transmission Coefficient. Within a canonical TST or VTST
framework, quantum tunneling is taken into account by a
temperature-dependent transmission coefficient k(T):
6-311G(2d,d,p)a
CBS-QB3a
G3MP2B327
14.1
14.6
14.7
15.0
15.8
16.1
21.3
22.0
23.5
23.2
22.8
23.9
This work.
2. COMPUTATIONAL DETAILS
Electronic Structure Calculations. Potential energy and
molecular properties of stationary points were calculated using
Gaussian 03 revision B.0333 and QChem version 3.1.34 For all
stationary and critical structures, geometry optimizations were
performed at the B3LYP/6-311G(2d,d,p) level of theory.35,36
Frequency calculations were performed at the same level of
theory for all optimized geometries to determine the nature of
stationary points. The composite CBS-QB3 method was applied
for all stationary geometries and transition states.37 The CBSQB3 model involves a five-step calculation starting with a
geometry optimization and a frequency calculation (scaled by a
factor 0.99) at the B3LYP/6-311G(2d,d,p) level of theory,
followed by single point energy calculations at the CCSD(T)/
6-31G(d0 ), MP4SDQ/cbsb4, and MP2/cbsb3 and a complete
basis set extrapolation to correct the total energy. Dynamic calculations along the reaction path were performed at the B3LYP/
6-311G(2d,d,p) level of theory. We found that for reactions
examined here, the energy barrier heights with zero-point energy
kT kTAeE=T
15
n PE Eqn , J
16
NE, J
hFE, J
17
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18
One-dimensional transmission coecients were also computed using Wigner and Skodje and Truhlar approximations
directly from CBS-QB3 results on stationary points of the PES.
The one-dimensional Eckart transmission coecients were calculated using ChemRate software where the characteristic length
of the Eckart function is obtained from forward and reverse
barrier heights (E1 and E1) at 0 K along with the imaginary
frequency (i) of the transition state using the equations reported
by Johnston and Heicklen.51 Note that in Chemrate, canonical
transmission coecients are calculated by integrating microcanonical transmission probabilities over the Boltzmann-weighted
energy distribution. Lennard-Jones parameters were taken from
the JetSurF version 1.0 transport database.52,53 Calculated characteristic lengths, as well as parameters E1, E1, and i, are given in
the Supporting Information.
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300 and 400 K than the present results. In particular, their Eckart
transmission coefficients are larger than our values. This fact
highlights the strong sensitivity of Eckart k(T) to the barrier
height and the imaginary frequency, an issue to be discussed later.
Although the discrepancy between the Eckart and SCT
methods is small, the fundamental cause for the apparent agreement is clear. The Eckart method inherently underestimates the
tunneling probability by neglecting corner-cutting. In most cases,
this underestimation is balanced by the fact that the Eckart
function yields a potential energy curve narrower than the actual
PES, as illustrated in Figure 4, thus leading to an overestimation
of the tunneling probability. Hence, the good agreement between
Eckart and SCT transmission coecients is in many ways
fortuitous because of error cancellation in the Eckart approximation. For the same reason, the ability of the Eckart method in
reproducing the SCT results should not be generalized to other
reaction systems. For hydrogen shift reactions studied here,
however, the Eckart method is accurate.
Zhang and Dibble60 studied the impact of tunneling on
hydrogen-transfer isomerizations in n-propylperoxy radical
using multidimensional SCT calculations as well as the onedimensional, Eckart, and Wigner transmission coecients. They
reached a similar conclusion for their system. The Eckart method
works well as compared to the SCT result, but they cautioned
that the agreement may not be generalized to other systems.
Multidimensional tunneling calculations allow for the calculation of representative tunneling energies. This energy represents
the path with the greatest tunneling probability at a given
temperature. SCT representative tunneling energies for hydrogen transfers in n-heptyl radicals system are presented in Table 4.
Below 800 K, the representative tunneling energies are well
below the barrier top, and the tunneling paths can deviate
dramatically from the reaction path. As an example, Figure 5
presents the PES for 1-heptyl / 4-heptyl and the representative
tunneling energy at 300 K. Above 800 K, tunneling and reaction
paths are converging, and a one-dimensional approximation is
generally adequate. For large critical ring structures, for example,
6ps and 7ps, and at low temperatures, the representative tunneling energy is closer to the energy of the saddle point than for the
5ps or 5ss hydrogen shift. Hence, corner-cutting is enhanced for
the more strained transition state structures. It is for this reason
that SCT calculations show that the transmission coecient
increases with a decrease in the critical ring size. For example,
k(T) values are predicted to be 268 and 270 for 5ps and 5ss
H-atom shifts at 300 K, respectively. For 6ps and 7ps transitions,
k(T) values are notably smaller and equal to 30.8 and 14.3,
respectively. The dierence remains signicant until 800 K, the
temperature above which the transmission coecients are close
to unity.
We compare our SCT results to those of Zheng and Truhlar32
for 1-pentyl 5ps and 1-hexyl 5ps and 6ps H-atom shifts and those
for 1-butyl 5pp and 1-pentyl 6pp of Ratkiewitcz et al.29 As shown
in Table 5, k(300 K) values calculated for H-shift in the vemembered ring transition structure is in reasonably good agreement with literature values. For six-membered ring structures,
the k(300 K) value of Zheng and Truhlar is larger than ours by
about a factor of 3 and that of Ratkiewitcz et al. by a factor of 4.
Note that the Hessians were computed for all of the points along
the MEP in both Ratkiewitcz et al. and our SCT/VTST calculations. In particular, Ratkiewitcz et al. performed a considerable
number of force constant calculations along the MEP to ensure
convergence of SCT calculations (150 points on each side of
Table 2. CBS-QB3 Critical Energies (kcal/mol, 0 K) Computed for ips and iss Hydrogen Shift
species
7ps
6ps
5ps
n-hexyl
n-heptyl
14.7
15.3
15.0
22.1
22.0
n-octyl
14.5
15.0
22.0
n-pentyl
6ss
5ss
22.3
22.8
15.7
22.6
Wigner
S&T
Eckart
SCT
300
4.2
1.1 105
454
268
400
2.8
55.5
13.0
15.6
500
2.2
5.4
4.2
4.9
600
1.8
2.7
2.6
2.8
800
1.5
1.7
1.7
1.7
1000
1500
1.3
1.1
1.4
1.1
1.4
1.2
1.4
1.2
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Figure 3. Comparison of the transmission coecient k(T) for 1- and 2-heptyl radicals calculated using the Wigner, Skodje and Truhlar (S&T), Eckart,
and SCT approximations. Symbols are computed values. Lines are drawn to guide the eye.
Table 4. Representative Tunneling Energies (Ert) as a Function of Temperature Relative to the Vibrational Ground-State
Energy of the Saddle Point (E0Kq) for Hydrogen Shift in
n-Heptyl
E0Kq Ert (kcal/mol)
T (K)
5ps
6ps
7ps
5ss
300
400
8.1
5.1
2.3
1.3
2.3
1.7
4.0
2.3
500
1.8
0.7
1.5
2.0
600
1.0
0.4
1.0
1.7
800
0.3
<0.01
0.4
1.0
1000
<0.01
<0.01
<0.01
0.4
1500
<0.01
<0.01
<0.01
<0.01
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accurate. LCT tunneling, even for a few energy levels, does lead
to larger transmission coecients. For example, for 7ps H-atom
shift in 1-heptyl, the transmission coecient is increased by 17%
at 300 K and 41% at 250 K.
Eckart transmission coecients are known to be sensitive to
the energy barrier height and the imaginary frequency at the
reference
231
245
364
Ratkiewitcz et al.29
268
this work
114
38.5
Ratkiewitcz et al.29
30.1
this work
Figure 6. Sensitivity of Eckart transmission coecient computed with respect to (a) critical energy (E0Kq) and (b) the imaginary frequency (i) for 14
H-shift in 1-heptyl with the base case E0Kq and vi computed at the CBS-QB3 level of theory. Symbols are computed values. Lines are drawn to guide
the eye.
326
ARTICLE
Figure 7. Arrhenius plots of the high-pressure limit rate constant for hydrogen shifts in n-heptyl radicals.
ARTICLE
Figure 9. Arrhenius plots for the high-pressure limit rate constants of hydrogen shifts in n-octyl radicals. The bottom right plot represents branching
ratios computed for the thermal decomposition of 1-octyl radical.
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n
55
T (K)
1.36 10
21.02
787
300500
2.91 105
1.70
17 812
5002000
8.25 1024
2.53 105
10.61
2516
300500
1.45
11 209
5002000
504
17 898
300500
5002000
2.05 1054
6.87 105
20.69
1.59
2.25 1020
9.24
3235
300500
5.52 104
1.39
10 556
5002000
3.70 1024
4.05 105
1.23 1055
2.73 105
10.69
3235
300500
1.37
11 109
5002000
21.00
974
300500
1.65
17 718
5002000
303
18 575
300500
5002000
1.92 1054
1.24 105
20.51
1.66
8.65 1030
12.07
4658
300500
1.11 104
1.39
14 475
5002000
2.47 1021
9.49
2817
300500
5002000
6.94 10
3.23 1023
1.74 105
1.30
10 542
10.28
2608
300500
1.38
11 145
5002000
3.43 1055
2.37 105
20.84
1.65
799
17 731
300500
5002000
7.78 1025
10.68
2875
300500
4.38 10
1.49 1052
5.34 104
ring size
7
RSE (kcal/mol)
1.46
11 807
5002000
19.81
897
300500
5
6c
9.28 10
1.51 104
1.704
1.068
2431
1711
10.4
3.4
1.69
18 491
5002000
7d
1.12 104
1.118
1600
2.9
E = Eabs + RSE
ps
ss
11.7
12.6
ekB T S n
h
R
ps
ss
3.61
4.56
19
329
RSE in cycloalkanes54
reaction class
Eabs
RSE
5ps
22.1
11.7a
10.4
7.1
6ps
15.1
11.7a
3.4
0.7
7ps
14.6
11.7a
2.9
6.8
5ss
6ss
22.7
15.7
12.6b
12.6b
10.1
3.1
7.1
0.7
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Table 9. Contributions of Internal Rotor Losses to the Entropy of Activation in iab Hydrogen Shift
per rotor entropy loss ((Sq) = Sq/n,
number of internal
reaction channel
cal/(mol K))
10.00
14.02
3.33
3.51
10.23
3.41
17.79
3.56
14.57
3.64
11.27
3.76
3
6
13.08
19.83
4.36
3.31
18.80
3.76
16.08
4.02
11.57
3.86
18.07
4.52
14.41
4.80
3.61 ( 0.23
4.56 ( 0.22
4. CONCLUSION
The role of quantum tunneling in hydrogen-transfer isomerizations of linear alkyl radicals was studied in detail. Transmission
coecients are shown to require a multidimensional treatment
below 800 K. Only above 800 K is a one-dimensional treatment
appropriate. The Eckart method is shown to reproduce the
multidimensional transmission coecients over the entire temperature range, but the agreement is due to a favorable error
cancellation. The inability of the Eckart approach to account for
higher-dimensional tunneling eect is compensated by the
rigidity of the Eckart function, leading to a potential energy
curve narrower than the actual PES. Calculations show that
below 600 K the Eckart transmission coecient is highly
sensitive to the value of the imaginary frequency, and hence is
subject to the uncertainty in the electronic structure calculation.
Regardless, high-pressure limit rate constants calculated using
the classical transition state theory with treatment of internal
rotation and the use of Eckart transmission coecients and a PES
determined at the CBS-QB3 level of theory are in good agreement with literature data.
The present results are consistent with Tsang et al., who
concluded that a large body of literature data at low temperatures
(with small A factor and activation energy) can be reconciled
with high-temperature data by taking into account quantum
tunneling. Our calculations also conrm their observation that
tunneling is more pronounced with ve-membered ring transition structures than with six-membered ring structures. In
addition, hydrogen transfer through an eight-membered ring
transition structure is not competitive due to prohibitive entropy
eects.
The systematic study of isomerization reactions from n-pentyl
to n-octyl led to a large set of theoretical kinetic data that can be
rationalized within a reaction class approach. It is shown that the
transmission coecient can be treated as an explicit structure/
reactivity correlation parameter. This approach allows for a fast
and suciently accurate estimation of the impact of tunneling on
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ASSOCIATED CONTENT
bS
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
This work was supported by the U.S. Air Force Oce of
Scientic Research (AFOSR Grant Nos. FA9550-07-1-0168 and
FA9550-08-1-0040) and by the Combustion Energy Frontier
Research Center (CEFRC), an Energy Frontier Research Center
funded by the U.S. Department of Energy, Oce of Science, Oce
of Basic Energy Sciences under Award No. DE-SC0001198. Part
of this work was performed using HPC resources from GENCICINES (Grant 2011086686).
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