Quantum scattering calculations on the CH4+OH→CH3+H2O reaction

Gunnar Nyman and David C. Clary

Citation: The Journal of Chemical Physics 101, 5756 (1994); doi: 10.1063/1.467360
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 Quantum scattering calculations on the CH 4 +OH-+CH 3 +H 2 0 reaction
Gunnar Nyman and David C. Clary
Depanment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 lEW, United Kingdom
(Received 3 May 1994; accepted 17 June 1994)
Quantum scattering calculations on the CH4+OH-+CH3+H 20 reaction have been performed at
thermal energies. The rotating bond approximation is used, treating CH3 as a pseudoatom. The OH
rotation and a reactive C-H stretch of CH4 are treated explicitly as well as the bending motion and
one OH local stretch vibration of H20. Two potential energy surfaces are used. Both have accurate
reactant and product rovibrational energy levels for the modes explicitly treated in the scattering
calculations and incorporate the zero point energy of the other modes. They have correct bond
dissociation energies and transition state geometries in reasonable accord with ab initio data. Mode
selectivity is found: reactants in the ground rovibrational states produce ground state H20, and
vibrationally excited CH4 produces vibrationally excited H20. Reactant OH rotational excitation
decreases the reaction cross sections. Rate constants are obtained using an adiabatic approach to
account for all degrees of freedom not explicitly treated in the scattering calculations. Large
contributions due to tunneling are observed. The rate constants are in quite good agreement with
previous theoretical and experimental work.

I. INTRODUCTION Zhang and Zhang have obtained initial state-specific

Methane is a greenhouse gas which plays a significant
role in the heat balance of the atmosphere.' It is thus impor-
tant to assess the rate of removal of methane from the atmo-
sphere, for which the reaction of methane with hydroxyl
radicals
is recognized as the main process.' This reaction has accord-
ingly received much interest both experimentally'-10 and
theoreticallyY-16 In the present work, we study the dynam-
ics of this reaction with approximate quantum scattering
theory.
By 1990, the quantum mechanical treatment of reactive
scattering had progressed from the first accurate converged
cross sections for H+H2-+H2+H in 1976 17 to
F+H2-+HF+H.'8 The same year, the first quantum scatter-
ing calculations for realistic four-atom reactions in linear ge-
ometries were published.'9,2o The first quantum scattering
calculation for a four-atom reaction with nonlinear geom-
etries were carried out by Clary for the OH+H2=H+H20
reaction in 1991. 21 The method used in that work has since
been called the rotating bond approximation (RBA).22,23 In
its fullest form, the RBA involves explicit treatment of all of
the vibrations of OH, H2, and H20, and rotations of OH, via
close-coupling calculations. The rotations of H2 are treated
by using an adiabatic approximation.
Subsequent quantum calculations of four-atom reactions
have also focused mainly on the OH + H2 = H + H20 reaction
and isotopically substituted variants. 22,24-40 In the method of
Wang and Bowman, three radial distances are treated explic-
itly, while all internal angular degrees of freedom, including
the bending mode of H20, are treated adiabatically. Echave
and Clary have obtained state-to-state reaction probabilities
in accurate calculations for a total angular momentum J=O
and planar geometries, freezing the nonreactive OH bond. 28
thermal rate constants for the OH+H2 reaction treating five
degrees of freedom 38 and most recently treating all six de-
grees of freedom explicitly.39 Manthe, Seideman, and
Mille?7 have calculated cumulative reaction probabilities ex-
actly for J =0 and used these to obtain thermal rate constants
by invoking a J-shifting approximation. 41 Baer and co-
workers have applied a method35 in which the three radial
coordinates are treated explicitly while the three angular co-
ordinates are fixed during each collision, but varied between
collisions using a Monte Carlo scheme. Neuhauser has also
recently carried out calculations of initially state selected re-
action probabilities for J=O using a time dependent
method.40
Recently the RBA has been applied to other four-atom
reactions, including CO+OH-+H+C02,23 Cl+HOD(H20)
=HCl+OD(OH),42 HCl + OH(OD)-+Cl + H 20(HOD),42.43
and HBr+OH-+Br+H 20.43 The present study extends the
RBA to reactions involving more than four atoms. In the
scattering calculations, CH3 is treated as a pseudoatom Q,
whereby reaction (Rl) can be written
QH(v)+OHU)-+Q+H20(m,n).
The quantum numbers v, j, m, and n represent the QH vi-
bration, the OH rotation, the H20 bend, and a local OH
stretch of H20, respectively. These degrees of freedom and
the relative translation are treated explicitly in the scattering
calculations by using the RBA. All other degrees of freedom
are treated by an adiabatic approach, to be described later.
The present quantum scattering treatment of CH4 is ex-
pected to be reasonable as ab initio calculations show that at
the transition state, the methyl group has a very small barrier
to internal rotation,14 meaning that the main interaction with
OH is through the reactive hydrogen in CH4. Perhaps the
main effect of the methyl group comes from its contribution
to the change in zero point energy as the reaction proceeds.
This is accounted for by an adiabatic approach, which in our

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 G. Nyman and D. C. Clary: CH 4 +OH->CH 3 +H 20 reaction
implementation means that the interaction potential is de-
signed such that it contains the zero point energy of all
modes not treated explicitly in the RBA.
Some of the assumptions made in the RBA have previ-
ously been tested by comparing with accurate quantum scat-
tering calculations on the H+H 20-+H2+OH reaction with
planar geometry, where the rotations of both H2 and OH are
treated explicitly.28 It was found that the RBA gave quite
accurate reaction probabilities for reaction with vibrationally
selected states of H20. Furthermore, cumulative reaction
probabilities from RBA calculations for the
OH + H 2-+ H + H20 reaction, where the H2 rotations are
treated adiabaticalIy,25 are in good agreement with the full
dimensionality quantum mechanical calculations of Manthe,
Seide man, and Miller. 37
For an ABC + D = A B + CD reaction, the fullest form of
the RBA 24 treats explicitly all three vibrations of the reactant
ABC, along with the rotation of AB and the vibrations of
both AB and CD. Here the AB vibration is, however, not
treated explicitly as it has been experimentally observed for
CI and H atoms reacting with H 20 that the nonreactive bond
in H 20 acts largely as a spectator. 44 - 46 For the
OH + H2-+H + H20 reaction, the spectator behavior of the
OH bond has been verified theoretically.24,25,39 This is ex-
pected to be a good approximation also in reaction (Rl) as
the OH bond length is almost unchanged between reactant
OH and the transition state geometry.13,14
Two reduced dimensionality potential energy surfaces
(RDPs) are developed in the present work. We apply the term
"reduced dimensionality" as these surfaces are explicit func-
tions of a reduced number of coordinates. Both RDPs com-
bine an accurate potential function for H20 (Ref. 47) with a
London-Eyring-Polanyi-Sato (LEPS) function to describe
the C-H and OH reactive bonds. The potentials have accu-
rate reactant and product rovibrational energy levels, correct
bond dissociation energies, and transition state geometries in
reasonable accord with ab initio data. 13,14 As mentioned, they
also incorporate the zero point energies of all modes not
explicitly treated in the RBA calculations. The two RDPs
differ mainly in the barrier height such that one surface
RDPI has a vibrationally adiabatic ground state (VAG) bar-
rier height of 5.9 kcaVmol, which is in accord with the ab
initio calculations of Melissas and Truhlar. 14 For the other
surface RDP2, the VAG barrier height is 6.7 kcaVmol.
In our previous work on the HCl +OD (Ref. 42) and
HCl+OH (Ref. 43) reactions, we found mode-selective be-
havior. For instance, reactants in rovibrational ground states
were found to produce ground state products, and vibrational
excitation of the HCI reactant gave vibrationally excited wa-
ter molecules. These effects are also found in the present
study. Furthermore, for HCl+OH(j), it was found that the
reaction cross sections depend approximately on (2j + 1) -I .
The same effect is seen here for the OH +CH4 reaction
though it is not quantitatively reproduced, which we believe
relates to the much larger activation energy in the present
reaction.
The remainder of this paper is structured such that in
Sec. II, the RBA calculations and the adiabatic approach are
described. Section III contains a description of the potential
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5757
energy surfaces used. In Sec. IV, the calculation of rate con-
stants and tunneling is described, and in Sec. V, the results
are presented and discussed. Conclusions are offered in Sec.
VI.
II. THEORY
In this section, some aspects of the RBA calculations are
discussed. Also, the adiabatic approach which is used to ac-
count for the degrees of freedom not explicitly treated by the
RBA is described.
A. The RBA calculations
The RBA was developed to treat four-atom reactions and
has been well documented previously.2l,25,42 In the present
paper, the RBA is applied to the seven-atom reaction
CH4+OH-+CH 3 +H 20. From the point of view of the quan-
tum scattering calculations, the CH 4 moiety is treated as a
quasidiatom QH, where Q is a quasiatom with the mass of
CH3. In this way, the OH+CH4 reaction is effectively re-
duced to a four-atom problem. The effect of the other atoms
enters the scattering calculations only through adiabatic Zero-
point energy in the potentials we employ, which are de-
scribed in Sec. m. Therefore, the theoretical development for
the scattering calculations is essentially the same as that
given before and the reader is referred to Refs. 21 and 42 for
a description of this part of the theory.
For later ease of reference, we give the Hamiltonian used
in the RBA calculations42
A h tf2
2
h a h
2
[
2
2
H=-2p, ap2-2p,p2 arF +2p,p2 1(1+1)-0 +4'
2
3]
2
h 2
+ 2MR(p,O)2 (j -0, )+BoHl + V(p,a,e), (1)
which has three degrees of freedom, where
{ mQmHmOmH )113 /MIRi
p,=\mQ+mH+mo+mH ' p= V---;:- +---;:-,
Here J is the angular momentum operator associated with
OH, which has the rotational constant B OH ' 1 is the total
angular momentum, and 0 is the projection quantum number
of 1 and j (the rotational quantum number corresponding to
]) along R I . RI is the vector connecting the OH center of
mass with the QH center of mass and R I is the corresponding
scalar. R2 and R3 are the OH and QH internuclear separa-
tions, respectively. R is the distance from H in QH to the
center of mass of OH. e is the angle between R2 and R I · mA
is the mass of species A. Other symbols have their usual
meaning.
To derive the Hamiltonian in Eq. (1), the centrifugal sud-
den approximation (also known as the coupled states or lz
conserving approximation48,49) has been invoked, whereby 0,
is treated as a good quantum number. p is called the hyper-
 5758 G. Nyman and D. C. Clary: CH4 +OH->CH 3 +H2 0 reaction
radius and 0 is the hyperangle. By diagonalizing the Hamil-
tonian in Eq. (1) for fixed values of p and plotting the eigen-
values against P. the so-called hyperspherical adiabats are
obtained.
The R-matrix propagator method50•51 is used to solve the
close coupling equations for different fixed 0 values. for all
values of 1 contributing to the reactive scattering.
The R matrix is propagated from a small value of the hyper-
radius in the classically forbidden region out to some large
value such that the fonning reaction fragments appear inde-
pendent of each other. Boundary conditions are applied.
whereby the S matrix 51 for scattering between all energeti-
cally allowed states is obtained.
The probability of going from an initial state (v.j). to a
final state (m.n) is given by
pi. a
v,j-+m,n
= Isi.f!- 12
U,j-+m,n'
h
were Si.n . I
v.j-+m.n IS an e ement 0
. pJ.n<o
f the S matnx. .
v.j-+m.n IS
. d f pi.-a _pi.a hi h·
o btame rom v.j-+m,n - v.j-+m,n' W C IS va 1 lor our l·d &
Hamiltonian.
The transition probabilities are converted to detailed ro-
tating bond cross sections Uv,j-+m.n for going from an initial
state (v.j) to a final state (m. n) using the relation
7T J.n
( 2·+1)k2.£.J £.J (2J+l)Pv.j ..... m.n.
U u,j--+m,n
J V.l a i;;.lal
where
fL: is the reduced mass of the colliding system and E v •j is the
OH(j) + QH( v) energy. We use Eq. (3) without considering
symmetry. which is not needed as absolute cross sections are
not presented. The symmetry must be considered in calculat-
ing rate constants. which is described in Sec. IV.
The detailed cross sections in Eq. (3) refer to transitions
between the specified initial and final states. The state of the
adiabatically treated degrees of freedom is not explicitly
specified. In Sec. II B. it will become clear that these are in
their ground state and therefore our cross sections are closely
related to full-dimensionality calculations. where the CH4 re-
actant is initially nonrotating.
The detailed cross sections in Eq. (3) may be summed
over all final states {m. n} to obtain total cross sections for
reaction out of a specified initial state. This is done at several
places in this paper. Our cross sections are not directly com-
parable with otherwise detennined absolute cross sections.
Conversion procedures to obtain absolute cross sections for
anABC(m.n)+D--+AB(j)+CD(v) reaction has been dis-
cussed previously.22.31 The conversion essentially involves
summing the cross sections over the available energy levels
of the adiabatically treated degrees of freedom at the transi-
tion state and dividing by a weighted sum of initial states.
This is not done in the present qualitative investigation of
mode selectivity in the OH +CH4 reaction. but is accounted
for in the calculation of thermal rate constants.
We now discuss some aspects of the approximations
made here. in particular. in regards to the treatment of CH4 •
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TABLE 1. Values for several parameters used in the RBA calculations.'
Parameter Value
18.9 cm- 1
18
98
18
18
60-99
107.20
'Notation as in Ref. 42 except for BOH •
For all geometries relevant to this discussion. one of the
three principal moments of inertia is clearly smaller than the
other two. We therefore refer to the corresponding principal
(2) axis as the unique axis and note that in the RBA this is the R I
axis.
A particular feature of the RBA is that the rotation of OH
in the present reaction is treated explicitly. This allows the
study of mode-selective effects with respect to this rotation.
Treating this rotation explicitly without allowing it to couple
to other angular degrees of freedom. however. requires jus-
tification. First. the high symmetry of CH4 results in a quite
unhindered OH rotational motion about the unique axis at the
(3) transition state and thus. coupling of this motion to CH4 is
weak. This agrees with Melissa's and Truhlar's calculation of
the barrier height to internal rotation. which was found to be
only 0.02 kcallmol. 14 Second. while the OH rotational mo-
tion in a plane containing the unique axis is strongly coupled
(4) to CH4 at the transition state. this is approximately treated in
the RBA through the interaction with the reactive hydrogen
atom in CH4 .
Another aspect concerns the OH rotational energy asso-
ciated with its rotation about the unique axis. This energy is
conserved if the OH rotation about this axis is uncoupled
from CH4 and the average of the inverse of the OH moment
of inertia about it does not change as the reaction proceeds.
We expect this to be a reasonable approximation which jus-
tifies that in the RBA the initial OH rotational energy about
R J is conserved. whereby it does not contribute energy to. or
withdraw energy from. the reaction coordinate.
In the RBA calculations. the R-matrix propagation has
been initiated at a hyperradius p=7.0 A and tenninated at
p=26.0-30.0 A. One hundred and thirty-five to 165 sectors
were used and the transition probabilities were averaged over
the last 15-30 sectors.22 Some other numerical aspects are
given in Table I. For 1=0. the RBA cumulative reaction
probabilities. i.e .• reaction probabilities summed over all ini-
tial and final states. are converged to within 1% for all ener-
gies used here. State-to-state reaction cross sections are con-
verged to within 3%. The RBA calculations are performed
for 99 total energies in the range 0.01-0.99 eV for 0=0 and
for 18 total energies in the range 0.05-0.60 eV for 0*0.
B. The adiabatic approach
Most degrees of freedom in the CH4 +OH reaction are
not explicitly treated in the RBA. Instead they are treated by
a modified version of the adiabatic bend theory due to
 G. Nyman and D. C. Clary: CH 4 +OH-.CH 3 +H 20 reaction 5759

Bowman. 3o•52 Bowman's approach is to treat vibrational
stretch motions explicitly while bends are treated adiabati-
cally. In brief, the Schrodinger equation is solved approxi-
mately in two steps. First it is solved for the Hamiltonian
associated with the bending degrees of freedom for a poten-
tial that refers to fixed values of the radial coordinates. The
eigenvalues obtained are then added to the Hamiltonian for
the radial coordinates, for which the close coupling equations
are solved. This treatment implicitly assumes that the bend-
ing degrees of freedom instantaneously adjust to changes in
the radial coordinates, in the same way as the electrons are
taken to instantaneously adjust to nuclear motions in the
Born -Oppenheimer approximation.
The adiabatic bend treatment of Bowman is accurate if
the degrees of freedom not treated explicitly only influence
the reaction by supplying or withdrawing energy due to a
change in their frequency along the reaction path. The main
difference here is that the degrees of freedom we treat ex-
plicitly are two stretches and a bend. Both types of adiabatic
approaches have been shown to work well for the H2 +OH
reaction. 25 •37
Collectively denoting the adiabatically treated degrees of
freedom a and the others e, we may write
some unspecified state of the e modes), then the reaction
probability for some excited state of the a modes P n(E) is
found as
Pn(E)=Po(E-d€), (7)
where
(8)
d€= €!.n- €!.o·
is the energy difference at the transition state between the
excited state and the ground state of the adiabatically treated
degrees of freedom.
Using the energy shift approximation, the scattering cal-
culations need only be performed for the a modes in their
ground states. Therefore the known ground state eigenvalues
Ea.n=o are added to the ab initio values before these
are used to fit the RDP. In this way, Ha need not be diago-
nalized, a global potential energy surface is not needed, and
yet, an adiabatic treatment of all modes not treated explicitly
in the RBA is obtained at no additional computational ex-
pense. Details of how the zero point energy Ea.n=o is in-
cluded in the potential are found in Sec. III. The mentioned
energy shift is used in calculating rate constants as described
in Sec. IV.

(5) 111. POTENTIAL ENERGY SURFACES

where fIa is the Hamiltonian for the a modes. Ta is the
kinetic energy operator of these modes, and V(a;e) is the
potential energy surface, V(a;e) is a function of 15 coordi-
nates even though the ones associated with the e modes are
held fixed. To solve the Schrodinger equation for fIa repeat-
edly for different values of the fixed coordinates requires that
V(a;e) is globally known.
Obtaining an accurate potential energy surface in 15 di-
mensions is not realistic at the present time. Instead, we only
obtain a reduced dimensionality potential, which essentially
is a complete potential for the degrees of freedom treated
explicitly, but not for the others. This means that we are
forced to make approximations to the adiabatic treatment.
The ab initio potential energy information we have
available for reaction (Rl) are the barrier height, exothermic-
ity and harmonic vibrational frequencies of reactants, prod-
ucts, and transition state. 13 •14 With only this information, the
eigenvalues E a•n of fIa where n collectively labels the quan-
tum states of the a modes, are simply taken to be the sum of
the harmonic energies associated with each relevant vibra-
tional frequency, i.e.,
The two potential energy surfaces developed for the
CH4 +OH--.CH 3 +H20 reaction are modeled in a similar
way to what we have used previously for the
HX +OH=>X + H 20 (X=>CI,Br) reactions. 43 An important
difference is, however, that here the zero point energy of all
modes not treated explicitly in the quantum mechanical scat-
tering calculations is included in each potential energy sur-
face. The potentials we use are thus tailored to the present
calculations. While thus having the advantage of having at
least in an approximate way dealt with the zero point ener-
gies, the same potential is not necessarily applicable in other
types of calculations, including those involving isotope sub-
stitutions.
Each potential energy surface is expanded in the form
V= VLEPS(rOH, rHQ, rOQ) + VHp(rOH, row, rHH')
(9)
TABLE II. LEPS Morse parameters applying to both the RDPI and RDP2
potential energy surfaces (in atomic units). The Sato parameters is -0.0086
for RDPI and -0.015 83 for RDP2.

(6)
2.06161" 2.664 41b 1.832<
0.172 569 d 0.129085 b 0.16982<
Here Vi is a harmonic vibrational frequency and the sum is 1.010 67e 1.12542b 1.214f
over the adiabatically treated modes.
aFor C-H bond in CH4 (Ref. 7).
It is assumed that the reaction is dominated by the shape bFor the O-C bond in (CH 3hO (Ref. 71).
of the adiabatic potential associated with the ground states of <Diatomic OH (Ref. 47).
these degrees of freedom, such that reaction probabilities for dFor the C-H bond in CH4 adding zero point energy to spectroscopic dis-
sociation energy (Ref. 70).
excited states can be found by an energy shift eVaried to give QH frequency close to the frequency of the v3b mode of
approximation. 52 Thus, if the reaction probability is P o(E) at CH4 •
total energy E with the a modes in their ground states (and fTaken from Ref. 72.

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 5760 G. Nyman and D. C. Clary: CH 4 +OH ..... CH 3 +H 2 0 reaction

where rAB is the distance between atoms A and B. VLEPS is a TABLE III. Some characteristics of the RDPI and RDP2 potential energy
LEPS potential function 53 with parameters given in Table II. surfaces.
V HzO is a potential energy surface due to Murrell and
Saddle point geometry (A)
Carter47 that gives the vibrational energy levels for H20 ac- RDPI RDP2
curately and also gives a reasonable description of the disso-
rQH 1.282 1.286
ciation of H20 (the prime on the unreactive hydrogen in H20 1.179 1.181
rOH
is only used when needed for clarity). V OH is the potential rOH' 0.965 0.965
function in V H20 describing the two-body O-H interaction. It LHOH' 101° 101°
is subtracted out as such a term already exists in V LEPS' In LQHO 1800 180°
the potential for H 20 in Ref. 47 there is a term in Harmonic saddle point frequencies (em-I)
and one in r;w which have here been removed to avoid RDPI RDP2
an unphysical interaction in the CH40H potential when rHH' 2275i 232li
and rOH or rHH' and rOH' are quite large. This has no signifi- In-plane bend 469 469
cant effect on the vibrational energy levels of H20. Symmetric stretch 572 570
There is a single parameter to vary in the potential, viz. Out-of-plane bend 635 635
HOH bend 1548 1547
the Sato parameter in the LEPS function. The usual proce- OH stretch 3708 3706
dure is to vary this parameter to obtain a desired value for the
classical barrier height. Here it is instead varied to obtain Barrier heights (em -I)
RDPI RDP2
what we call a reduced dimensionality barrier (RDB) height
in that it is adapted to a quantum calculation treating explic- RDB 2573 2859
itly only a reduced number of degrees of freedom. The RDB VAG barrier 2063 2348
Scattering path 2581 2868
height is obtained by adding the zero point energy of all
modes not treated explicitly in the quantum scattering calcu- Reactant and product harmonic frequencies (cm -I)
lations, to the classical potential at the transition state and to RDPIIRDP2
the reactants at equilibrium. QH stretch 3140
The difference between the VAG barrier height and the OH stretch 3738
RDB height is just the zero point energy of the explicitly H20 bend 1611
treated modes. The only reactant mode treated in the RBA H20 stretch 3832
H20 stretch 3937
which contain zero point energy is the Q-H stretch. For the
transition state, the H 20 bend and the symmetric stretch of
the transition state (treated by the hyperradius) are the only
modes in the RBA which hold zero point energy. Accord- frequencies are 2275 and 2321 cm- I for RDPI and RDP2,
ingly, the VAG barrier height for each RDP is calculated respectively. The imaginary saddle point frequency obtained
from ab initio by Melissas and Truhlar is 1830 cm -1.14
In the scattering calculations, the H20 vibrational fre-
(10) quencies are calculated with OH held fixed and are therefore
not exact. For RDP1(RDP2), the fundamental bend fre-
where V* and V r denote the values of the RDP at the transi- quency is 1612(1612) cm- I for 0=0, which compares fa-
tion state, here placed at the saddle point, and for reactants at vorably with the experimental value of 1595 cm- I . 54 The
equilibrium, respectively. iig, ii;, and iiQH are normal mode fundamental local OH stretch frequency is 3700(3698) cm- I
frequencies and refer to the H20 bend at the saddle point, the for 0=0, in good agreement with the average of the experi-
symmetric stretch of the transition state, and the QH stretch mental symmetric stretch frequency 3657 cm -1 and asym-
of the reactants, in that order. metric stretch frequency 3756 cm- I of H20.54 The HQ fun-
For RDPI, Eq. (10) gives a VAG barrier height of 5.90 damental frequency is 3007(3006) cm -I, which agrees well
kcalJmol, which agrees with the value quoted by Melissas with the experimental value 3019 cm- I for the triply degen-
and Truhlar ll (referring to their second-order erate normal modes V3b of CH4, where a CH stretch is
(MP2)/adj-cc-pVTZ calculations). For RDP2, the VAG bar- identified. 54
rier height is 6.71 kca1/mol. 13 In Table III, some characteris- The reaction path in the scattering calculations does not
tics of the potential energy surfaces are given. follow the minimum energy path. From Table III, it is, how-
The ab initio calculations by Melissas and Truhlar l4 give ever, seen that the barrier along the scattering path is within
for the saddle point geometries in Angstroms and degrees 10 cm -1 of the saddle point value. The
rQH=1.l9, rOH=1.30, rOH,=0.970, LHOH=97.1, and QH(v=0)+OH(j=0)-->Q+H20(0,0) reaction is 0.583 eV
LQHO= 170. This compares reasonably well with the values exoergic in the scattering calculations on both RDPI and
in Table III. We note, however, that for our potentials RDP2, in agreement with ab initio calculations and the ex-
r QH > r OH' which agrees with the ab initio calculations at the perimental exotherrnicity.13
Hartree-Fock level, but not when electronic correlation is
included. 14 It should also be noted that our saddle point ge- IV. RATE CONSTANTS AND TUNNELING
ometries refer to potentials which contain the zero point en- A convenient expression. for the thermal rate constant
ergy of the modes not treated in the RBA. The imaginary is 55 •56

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 G. Nyman and D. C. Clary: CH4 +OH-+CH 3 +H 2 0 reaction 5761

+OO

f
(16)
k(T)=[21TfiQr(T)r 1 -00 dE exp(-ElkT)N(E),

(11)
where e'r!is the symmetric top rotational energy of the tran-
sition state given by
where T is the temperature, E is the total energy, Qr( T) is
(17)
the reactant partition function per unit volume, and N(E) is
the cumulative reaction probability obtained by summing the where Bave=(B+ C)12, and A, B, and C are rigid rotor con-
state-to-state reaction probabilities over all final and all ini- stants. Inserting Eqs. (16) and (17) in Eq. (14), it is straight-
tial states at a certain total energy. forward to obtain
Cumulative reaction probabilities from the RBA calcula-
tions NRBA(E) are only summed over the states treated ex- Q'(T) f+oo
k(T) =21TfiQ/T) -00 dE exp(-ElkT)
plicitly in the scattering calculations. An approximation to
the exact N(E) is obtained by convoluting NRB\E) with the
density of states of the remaining modes P(E). Thus XNRBA(E,J=O, K=O), (18)
where
N(E)= foE dE'NRBA(E')p(E-E'), (12)
(19)

which is equivalent to the energy shift approximation intro- and

duced in Sec. II B. If NRB\E) in Eq. (12) is replaced by a co J
sum of states for the corresponding modes, one obtains the
convolution integral often used to obtain the sum of states
Q;ot= 2: (21+ 1) 2: exp( - €:!lkT) (20)
J=O K=-J
over several degrees of freedom, for instance, in unimolecu-
lar reactions. 57 is the rigid rotor symmetric top approximation for the rota-
Inserting Eq. (12) into Eq. (11), changing the order of tional partition function of the CH40H complex. Equation
integration and introducing E" = E - E' gives (18) is used to obtain rate constants in the J-shifting approxi-
+OO
mation.
k(T)=[21TfiQr(T)r 1
f
-00 dE' exp(-E'/kT) In all calculations to be reported, Q(T) and Qr(T) were
evaluated in the harmonic oscillator-rigid rotor approxima-
tion. In Sec. V C, the lowest frequency mode at the transition
oo
XNRBA(E') fo dE"p(E")exp(-E"lkT). (13) state was treated as a one-dimensional hindered internal rotor
as described by Truhlar. 58 The moment of inertia for the in-
ternal rotation was set to 7690 a.u. and the symmetry to 3. 14
In Eq. (13), the second integral is identified with the partition
Otherwise, symmetry is not considered when evaluating the
function Q(T) for all modes not treated explicitly by the external rotational partition functions (which were evaluated
RBA which gives by summing over the rotational energy levels). Instead the
Q(T) f+oo rate constant expression in Eq. (14) or Eq. (18) is multiplied
k(T) = 21TfiQr(T) -00 dE exp( - ElkT)NRBA(E) , by a factor 12.14 The geometry and vibrational harmonic fre-
quencies for the eclipsed transition state obtained ab initio
(14)
(at MP2Iadj-cc-pVTZ level) by Melissas and Truhlar l4 were
where the superscript prime has been dropped. This expres- used, and similarly for the reactants. This gives (in cm - I)
sion is evaluated to obtain the thermal rate constant in our 4.07,0.313, and 0.308 for the rotational constants at the tran-
full centrifugal sudden calculations. sition state and 5.35 for CH4, while the one for OH is as in
To obtain NRBA(E), scattering calculations for all con- Table I.
tributing values of J and n have to be performed. We have The use of symmetry numbers results from assuming
therefore applied the "J-shifting" approximation,41 whereby that nuclear spin is separable from rotation. With the aid of
actual scattering calculations need only be performed for Ref. 59, we have evaluated the coupled nuclear spin-
J =0. We find that this approximation works well, which is rotational partition function for CH4, taking the 16 (24) low-
shown in Sec. V B. It is now described how the J-shifting est nuclear spin functions to be degenerate and others not to
approximation has been used to obtain the rate constants contribute at all. We find that separating the nuclear spin and
presented in Sec. V C (this procedure differs in detail from rotational partition functions is accurate to within 1% at 40 K
that used in Sec. V B). and excellent at the temperatures considered here.
CH40H at the transition state is treated as a symmetric Q(T) refers to the vibrational degrees of freedom not
top and we identify n with the symmetric top rotational treated in the RBA at the transition state. It therefore contains
quantum number K. In obvious notation neither the symmetric stretch of the transition state complex,
00 J which is treated by the hyperradius in the RBA, nor the
NRBA(E) = 2: (2J+ I) 2: NRBA(E,J,K). (15) mode which is largely a H 20 bend. From ab initio calcula-
tions using CADPAC,60 we identified these two modes with
J=O K=-J
the frequencies 769 and 1414 cm- I of Melissas and
lnvoking the J-shifting approximation gives Truhlar,14 respectively.

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 5762 G. Nyman and D. C. Clary: CH 4 +OH-+CH 3 +H 20 reaction

A final point to note regarding the rate constant is that where E* is the J dependent vibrationally adiabatic thresh-
OHen) has four thermally accessible electronic states occur- old energy (since we are considering reaction out of the
ring in two degenerate pairs (neglecting A doubling) sepa- ground state, only 0.=0 is needed). Again carrying through
rated due to the spin-orbit coupling. The energy difference the derivation from Eq. (11) to Eq. (14) and then invoking
was here set to 181 K, which allows for the difference in the J -shifting approximation, which in Sec. V B will be
rotational motion between the spin-orbit split states. One of shown to work well, Eq. (21) can be transformed into
the upper and one of the lower states correlate with a 2A"
surface and the other two with a 2A' surface of the CH 40H G_ dE exp(-ElkT)NRBA,G(E,J=O, K=O)
complex assuming C s symmetry, which is found by Melissas - +00 RBAG •
f/J.vvAGdEexp(-ElkT)N '(E,J=O, K=O)
and Truhlar at the transition state. 14 We assume that the 2A" sp
(22)
surface is well above the 2A' surface in the transition state
region. Assuming electronic adiabaticity leads us to mUltiply We also define a ground state transmission coefficient KG
the rate constant in Eq. (18) by a temperature independent which is obtained from Eq. (22) by the denominator setting
factor of 112 and leaving out the electronic partition function
in the denominator. The same temperature independent factor NRBA,G(E,J=O, K=O)== I, for E>6. (23)
of 112 is obtained if the electronic partition functions are
evaluated explicitly and it is additionally assumed that the This gives
spin-orbit coupling yields the same energy splitting at the
transition state as it does for reactant OH.
Next the ground state tunneling coefficient (G denot-
K
G= kIT exp ( 6. J:: dE exp( - ElkT)

ing the ground state) is defined as the ratio of the thermal
rate constant out of the ground state to the thermal rate con-
stant out of the ground state obtained if reaction probabilities
below the vibrationally adiabatic threshold are set to zero.
Denoting cumulative reaction probabilities out of the ground
state NG(E), it is seen from Eq. (11) that can be written
G_ dE exp( - ElkT)NG(E)
(21)
- f;: dE exp( - ElkT)NG(E) ,
XNRBA,G(E,J=O, K=O). (24)
The transmission coefficient thus gives the ratio of the
quantum mechanical ground state rate constant to the one
where no tunneling occurs and there is no reflection at ener-
gies above the adiabatic ground state barrier, which is in
agreement with previous usage. 61
Convergence tests suggest that presented values for
KG, and thermal rate constants obtained using the J -shifting

45

20

15 (0,0)

Ul
Ul
o
I-l
u
10
>::
o
...,
'M
U
m
(])
Ix<
5

o L______ )
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Etrans/eV

FIG. I. Reaction cross sections for CH4(v=0)+OH(j=0)-+CH3 +H20(m,n) as a function of translational energy on RDPI. State selected cross sections
are labeled (m,n). The curve labeled "total" represents cross sections summed over all product states.

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 G. Nyman and D. C. Clary: CH 4 +OH--.CH 3 +H 20 reaction 5763

10000

8000

6000

.-i
I
e 4000
u
......
>.
0-
J.l
Q)
c 2000
P'l

(0,1)
a (2, 0)

(1, 0)
-2000

(0, 0)
-4000
10 15 20 25 30

Hyperradius/bohr

FIG. 2. Hyperspherical adiabatic energy levels for the CH4 +OH=CH3 +H20 reaction for !l=O as a function of the hyperradius on RDPI. The four lowest
adiabats correspond to H20 states at large values of p, as labeled. The next adiabat corresponds to the CH4(v =O)+OH(j=O) state at large values of p. The
dashed curve marks the potential ridge.

approximation are converged to within = 1%, while thermal
rate constants obtained from full centrifugal sudden calcula-
tions are converged to within 2%.
v. RESULTS AND DISCUSSION
A. Cross sections and mode selectivity
In this section, reaction cross sections obtained using Eq.
(3) are reported. In Fig. I, detailed reaction cross sections for
the CH4 (u =0)+OH(j=0)-+CH 3 +H 20(m,n) reaction on
RDPI are shown as a function of translational energy. It is
seen that H20 is almost produced exclusively in its ground
vibrational state up to 0.4 e V translational energy and this
product state clearly dominates over the whole energy range
shown.
From the cross sections in Fig. 1, it is clear that there is
an activation energy associated with the
CH4 (u =O)+OH(j=O) reaction, which results from the VAG
barrier of 0.256 eV. This can also be inferred from the hy-
perspherical adiabats shown in Fig. 2. There is an avoided
crossing between the curves with reactant and product
ground state character close to the ridge at p=9.5 bohr. This
avoided crossing is clearly above the energy of the reactants,
giving an activation barrier. The fact that it is the ground
state curves which encounter an avoided crossing explains
the production of ground state products. The significance of
the ridge and the avoided crossings for heavy-light-heavy
(HLH) reactions have been discussed previously.42,43,62
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We have previously found that the HCI(u =O)+OD(j
=0) (Ref. 42) and HCI(v=O)+OH(j=O) (Ref. 43) reactions
mostly produce vibrational ground state water molecules, as
is also found here for the CH4 (u =O)+OH(j=O) reaction.
These reactions are of the HLH type and have similar exo-
thermicity (=0.6 eV). The Hz{u =O)+OH(j=O),
H 2(u =O)+OD(j=O), D 2 (u =O)+OH(j=O), and
HBr(u =O)+OH(j=O) reactions on the other hand produce
vibrationally excited water molecules.24,26,43 The HBr+OH
reaction is of the HLH type, but it has an exothermicity of
about 1.3 eV.43 The vibrational state of the H20 product can
be understood from the hyperspherical adiabats.
In Fig. 3, detailed reaction cross sections for the
CH4 (u=1)+OH(j=0)-+CH 3 +H 20(m,n) reaction on RDPI
are shown as a function of translational energy. It is notice-
able how the product (0,1) and (1,1) states are preferentially
populated. Thus the initial quantum of energy in the breaking
bond of CH4 is transferred to the forming OH bond in H20.
This behavior is analogous to what we observed for the HCI
+OD-+CI + HOD reaction, where initial excitation of the
HCI bond is transferred to the local OH stretch in HOD. 42
For the H2(u=1)+OH(j=0) reaction on the other hand, the
(0,2) state of H20 dominates. 26
In Fig. 4, detailed reaction cross sections for the
CH4 (u=0)+OH(j=1)-+CH 3 +H 20(m,n) reaction on RDPI
are shown as a function of translational energy. Figure 4 is
based on results from n=o (1/3 weight) and n= 1 (2/3
weight) calculations. As in Fig. 1, H20 is preferentially pro-
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 5764 G. Nyman and D. C. Clary: CH 4 +OH .....CH 3 +H2 0 reaction

30

total

25

;:l

m
"-
0
20
'M
+l
0
Q)
Ul

Ul 15
Ul
0
1-<.
0
(0,1)
I:::
0
·M 10
+l
0 (1,1)
m
Q)

(0,2)
(1,0)
0
0 0.1 0.2 0.3 0.4 0.5
Etrans/eV

FIG. 3. Reaction cross sections for CHiv= 1)+OH(j=0) ..... CH 3 +H 20(m.n) as a function of translational energy on RDPI. State selected cross sections
are labeled (m.n). The curve labeled total represents cross sections summed over all product states.

25

total
20

(0,0)
15

10

5
(1,0)

(0,1)
o 2 0
o 0.1 0.2 0.3 0.4 0.5 0.6
Etrans/eV

FIG. 4, Reaction cross sections for CHiv=O)+OH(j=1) ..... CH 3 +H20(m.n) as a function of translational energy on RDPI. State selected cross sections
uv=o,j= are labeled (m.n). The curve labeled total represents cross sections summed over all product states.

J. Chern.
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 G. Nyman and D. C. Clary: CH4 +OH->CH3 +H 20 reaction 5765

tions when averaged over 0 (the j =0 cross sections must be

divided by two for this to hold).
For the OH+CH4 reaction, there is at low energies a
quite strong increase in the j = 101 cross sections with j,
which is illustrated in Fig. 7. This is due probably to the
large activation energy present in the CH4 +OH reaction,
whereby the increase in total energy with increasing j en-
hances reaction. The combination of the two effects now
discussed produces the j dependence seen in Fig. 5.

B. The J-shlftlng approximation

0 In this section, we compare NRBA(E,J,K) obtained from
0.1 0.2 0.25 0.3 0.35 0.' 0.45 0.5 0.55 0.0
Etrans/ev
centrifugal sudden calculations with the ones obtained using
the J-shifting approximation. In making this comparison, the
J -shifting approximation is implemented to conform to the
0.1
(b) energy levels for external rotation produced by the RBA
0.7 Hamiltonian in Eq. (1) at the barrier in the potential along
the scattering path. These levels depend on the values of 1
0.'
P
and O. Remembering that operating with results in a pro-
0.5 jection 0 2 along R I , the rigid rotor levels obtained from Eq.
···•
§
0 ••
(1) are seen to be
11,2
c
j
0.3 [J(J+ 1)-02]+B oH0 2, (25)
f..LP s
.;
0
0.2
where Ps is the value of the hyperradius at the scattering path
0.1
barrier and a reference level tfXl=O is assumed.
0
The energy levels of Eq. (25) are identical to those of a
0,07 0.09 0.1
0.05 0.06 0.08 0.11 0.12 0.13 0.14 0.15
prolate symmetric top with rotational constants
Etrans/ev'
B=C=1I,2/(2f..Lp;) and A=B oH . For RDPl, Ps=9.4652
bohr giving B=0.345 cm- I . The J shifting is performed as
FIG. 5. Reaction cross sections for CHiv=O)+OHU)->CH)+HzO described in Sec. IV, but using the rotational constants just
summed over all product states and averaged over 0 are shown as II function given and identifying 0 with K.
of translational energy using RDPI. The value of j is indicated for each
curve in (a) and the order is the same in (b).
In Fig. 8, NRBA(E,J,K=O) is shown as a function of J
for RDPI for three values of the total energy, which is mea-
sured from the CH4 +OH ground state. Centrifugal sudden
duced in its vibrational ground state. The most significant results (for O=K) are compared with results from the RBA
difference to the CH4 (v=0)+OH(j=0)-+CH3 +H 20(m,n) adapted J -shifting approximation. The agreement is seen to
reaction is the larger population in the product (1,0) state, be good.
which results from the 0=0 contribution to the In Fig. 9, N RBA(E,J,K=3) is shown as a function of J
CH4(v=0)+OH(j=I) cross sections. Again, this is similar for RDPI for three values of the total energy. Results from
to what we observed for the HCI +OD reaction. 42 the RBA adapted J-shifting procedure setting 0=3 in Eq.
In Fig. 5, reaction cross sections for RDPI out of the (25) are compared with centrifugal sudden results for 0=3.
=O)+OH(j) states for j:S;.7 are shown as a function of Again, the cumulative reaction probabilities in the J -shifting
translational energy. These cross sections are summed over approximation, which are based on scattering calculations
all product CH 3 +H 20 states and averaged over O. They are for 1=0=0 only, are in good agreement with the centrifugal
seen to decrease with j, which results from averaging them sudden ones, which result from explicit scattering calcula-
over 0 as will be illustrated next. tions for all relevant values of J for, in this case, 0=3.
The cross sections are large for reaction out of OH(j The results in Figs. 8 and 9 suggest that the J -shifting
=101), but smaller when j>IOI. At the energies most impor- approximation works well for all translational and rotational
tant for the thermal rate constant at room temperature, the energies important in calculating the thermal rate constant
differences are quite large, which is illustrated in Fig. 6 for and should thus be most useful for this purpose. To investi-
j =I, 2, 3, and 7. This is also in agreement with our obser- gate this, an explicit calculation of the thermal rate constant
vations for the HCI +OH and HBr+OH reactions. 43 For will be presented. To do this, we note that the RBA treats the
these two reactions, which have no or small activation en- OH rotation about RI as uncoupled from the methyl rotation
ergy, the j=IOI cross sections (which are summed over all about this axis. In calculating full centrifugal sudden rate
product states, but not averaged over 0) are further rather constants, these rotations should thus appear as two free one-
independent of the value of j. This leads to an approximate dimensional (ID) rotors in Eq. (14), where the methyl rota-
r
(2j + I I dependence of the low energy reaction cross sec- tion appears in Q and the OH rotation and orbital motion is

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 5766 G. Nyman and D. C. Clary: CH 4 +OH-+CH 3 +H 20 reaction

30 30
c.) j-l Ib) j-2

25 2.
,;
.:i
20 20

:
15 15

c
10
.!l 10
j

0 0
0.1 0.15 0.2 0.25 0.3 0.35 0.' 0.45 0.' 0.55 0.' 0.1 0.15 0.2 0.25 0.3 0.35 0.' D.tS 0.' 0.55 0.1
stuns/eV Itrans/.V

30
Ce, j-3 30
(d) j-7

, 25
25
.:i
20
i 20
: 1l
·e
u
15
:
15
c
0

·
u 10
u 10

0
0.1 0.15 0.2 0.25 0.3 0.35 0
0.' 0.45 0.' 0.55 0.0 0.1 0.15 0.2 0.25 0.3 0.35 0 •• 0.45 0 ••
Etrana/.V
Etrana/.V

FIG. 6. Reaction cross sections for CH4 (v =0) +OH(j ,,n)-+CH3 + H 20 summed over all product states are shown as a function of translational energy using
RDPl. The value of j is indicated to the left in each panel. The value of,n is indicated to the right in each panel.

7
30 6
5

25
::s 1
III 0
'-
I'::
0
rf 20
C)
Q)
Ul

Ul
Ul
0 15
I.e
C)

I'::
0
·rf
C)
10
III
Q)

o
0.1 0.15 0.2 0.25 0_3 0.35 0.4 0.45 0.5 0.55 0.6
Etrans/eV

FIG. 7. Reaction cross sections for CHiv =0)+OH(j=!1)-+CH 3 +H20 summed over all product states are shown as a function of translational energy using
RDPJ. The value of !1 is indicated for each curve.

J. Chern. Phys., Vol. 101, No.7, 1 October 1994

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 G. Nyman and D. C. Clary: CH 4 +OH ....... CH 3 +H 2 0 reaction
0.7
0.6
0.5
0.2 eV
u 0.4
I
I<t!
0.3
0.2
0.15 eV
0.1
0
0 10 20
FIG. 8. NRBA(E,J,K) calculated on RDPI using the centrifugal sudden approximation (solid lines) are compared with results from the RBA adapted J-shifting
approximation (dashed lines) for three energies as indicated (K=O).
part of the integral. This picture, with two ID rotations, is
equivalent to that of an external rotation for a rigid CH40H
complex about RI combined with a free internal rotation.
To make the evaluation of the rate constant in the
J-shifting approximation in Eq. (18) consistent with that of
the centrifugal sudden evaluation in Eq. (14), Q' contains
free ID rotations of both OH and the methyl group and also
orbital motion. The rotational constants for OH, the methyl
group, and orbital motion were here set to 18.9, 5.35, and
0.345 cm -I, respectively. The symmetry number for the me-
thyl rotation is 3. The modes treated as pure vibrations are as
given in Sec. IV.
In Table IV, thermal rate constants in the J-shifting ap-
proximation are compared to centrifugal sudden ones, in
both cases obtained using the procedures just described.
RDPI was used and the temperature range is 178-420 K.
The J -shifting approximation is seen to give thermal rate
constants in good agreement with the centrifugal sudden
ones, as anticipated from Figs. 8 and 9. Though not seen
from Table IV, the agreement is better than 10% up to at
least 800 K.
The J -shifting approximation41 has been found to work
excellently for H + H2 (Ref. 41) and D+ H2 (Ref. 63) in com-
parison with exact calculations of Chatfield et al. 64 and
Zhang and Miller. 65 Auerbach and Miller recently tested the
J-shifting approximation for the D+ H2(v = 1) reaction up to
700 K and found that it gives rotationally averaged rate con-
stants in quite good agreement with exact calculations.66
The J -shifting approximation has also been examined by
Moribayashi et at. 67 and Mielke et ai. 68 for D + H2 and they
suggest improved versions which, however, require input
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5767
30 40 50 60
J
from accurate calculations for J>O. We find in comparing
with centrifugal sudden calculations that the J -shifting ap-
proximation works well, both for K=O and K,*O. Consider-
ing the substantial savings in computer time, we will there-
fore in Sec. V C use the J -shifting approximation to calculate
thermal rate constants as described in Sec. IV.
c. Rate constants and tunneling
In this section, thermal rate constants and tunneling and
transmission coefficients are presented. In Fig. 10, the loga-
rithm of the thermal rate constant is shown vs inverse tem-
perature. Rate constants calculated for RDPI and RDP2 are
compared with experimental results by Vaghjiani and
Ravishankara, l Dunlop and Tully,1O and Sharkey and Smith. 8
Also included are variational transition state theory (VTST)
results by Melissas and Truhlar 14 for a potential with the
same VAG barrier height as RDPI.
The agreement is quite good between the rate constant
calculated on RDP2 and the experimental ones by Vaghjiani
and Ravishankara, and Dunlop and Tully. In particular, no-
tice the good agreement in slope between these rate con-
stants. Nonadiabatic transitions give rise to a very non-
Arrhenius form for the thermal rate constant. 69 The results in
Fig. 10 thus suggest that nonadiabatic transitions are unim-
portant for the OH +CH4 reaction.
At 300 K, our rate constant on the RDPI surface is
larger than that of Melissas and Truhlar by a factor 2.3. This
may be due largely to the use of different potentials, even
though the VAG barrier height is the same, and is consistent
with the larger imaginary frequency on RDPI than found ab
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 5768 G. Nyman and D. C. Clary: CH 4 +OH ..... CH3 +H 20 reaction

0.7

0.25 eV
0.6

0.5

&!
u 0.4
1
tcI!
f!1
p:;
0.3 0.2 eV
_- .. _- .......................
...

0.2
-------,
"''''...

0.1
0.15 eV

0
0 10 20 30 40 50 60
J

FIG. 9. NRB\E,J,K) calculated on RDPI using the centrifugal sudden approximation (solid lines) are compared with results from the RBA adapted J-shifting
approximation (dashed lines) for three energies as indicated (K=3).

initio.14 We notice that the slope obtained in the VTST by the difference in barrier height between RDP1 and RDP2.
calculations 14 is different from ours and the experimental This difference is close to that found between the ab initio
ones,I,1O in particular, at low temperature. In part, this results calculations by Melissas and Truhlar l4 and Dobbs et al. 13
from the treatment used for the electronic partition function using large basis sets and correlated wave functions.
in the VTST calculations, which neglects spin-orbit splitting The importance of tunneling is explicitly demonstrated
at the transition state, but includes it for the OH reactant. in Table V where the tunneling and transmission coefficients
Figure 10 shows that the calculated rate constants at 300 are given for a set of temperatures for both RDPI and RDP2.
K differ by a factor 2.6 between RDP1 and RDP2. This Transmission coefficients were calculated by Melissas and
uncertainty in the calculated rate constant will be very diffi- Truhlar for a potential with the same VAG barrier height as
cult to improve on as the barrier height cannot be determined
that of RDPI. They obtained values of 8.7, 1.6, and 1.1 for
at present to substantially higher accuracy than what is given
the transmission coefficient at 300, 600, and 1000 K,
respectively. 14 Our corresponding values are 22, 2.9, and 1.4.
At 300 K, the ratio between our value and that of Melissas
TABLE IV. Thermal rate constant for the CH4 +OH ..... CH 3 +H 20 reaction
(em3 S-I) on RDPI. Details are in the text. and Truhlar is 2.5, which is essentially the ratio of the ther-
mal rate constants given above and is again consistent with
T(K) C.S." J shiftb our larger imaginary frequency. It is clear that tunneling
178 4.4( -16)< 4.0(-16) should be accounted for in any theory, which is applied to the
216 1.5( -15) 1.4( -15) OH +CH4 reaction.
223 1.8( -15) 1.6( -15) In Fig. 11, RBA reaction probabilities for RDPI out of
250 3.4( -15) 3.2( -15)
273 5.5( -15) 5.3( -15) CH4 (v =O)+OH(j =0) summed over all product states are
300 9.2( -15) 8.7( -15) shown as a function of total angular momentum for a range
350 2.0( -14) 1.9( -14) of total energies. It is seen that the reaction probability never
400 3.7(-14) 3.6( -14)
reaches 0.7. In transition state theory, the reaction probability
420 4.7(-14) 4.5(-14)
is set to unity at energies above the VAG threshold. At low
"Pull centrifugal sudden calculation. NPB\E) summed up to il=8, includ- temperatures, this has a very small effect on the rate con-
ing energies up to E=0.6 eV. Extending these ranges should increase ken stant, where tunneling is the dominant contribution. At
at most I % at 420 K and less at lower temperature.
"The RBA adapted J -shifting approximation invoked. higher temperatures, it contributes to an overestimation of
<Power of 10 in parentheses. the rate constant.

J. Chern.
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 G. Nyman and D. C. Clary: CH4 +OH ....... CH 3 +H 20 reaction 5769

-12
RDP2
RDP1
-12.5 Truhlar
Ravishankara
Tully
Smith -<)-.-

-13
,
......
0
<li
...... -13.5
0
E
,
......
IJ)
«) -14
E
0
"E-<
-14.5
..I<
tl\
0
.--f
-15

-15.5

-16
1.5 2 2.5 3 3.5 4 4.5 5 5.5
1000/T

FIG. 10. The logarithm of the thermal rate constant vs inverse temperature (K-'). Our calculated results are for the potential energy surface indicated in the
key and using the i-shifting approximation. The other results are from VTST calculations by Melissas and Truhlar (Ref. 14) and experimental work by
Vaghjiani and Ravishankara (Ref. I). Dunlop and Tully (Ref. 10) and Sharkey and Smith (Ref. 8).

VI. CONCLUSIONS HCI +OD reaction. 42 In fact, the patterns found for the vibra-
tionally selected dynamics of heavy-light-heavy atom-
The rotating bond approximation has been applied to the
diatom reactions have been found in HLH four-atom
CH 4 +OH-+CH 3 +H 20 reaction. The scattering calculations
reactions,25,43 and from the present work, the same principles
are performed within a model which treats CH3 as a
seem to extend to even larger HLH reactions.
pseudoatom and CH4 as a pseudodiatom. The rotation of OH,
It was shown that the reaction cross sections for OH(j
a reactive C-H stretch of CH4, two vibrations of H20, and
=101) are substantially larger than those for OH(j>IOI), in
relative translation are treated explicitly in the scattering cal-
agreement with previous work for HCI+OH and
culations. An adiabatic approach is used to account for all
HBr+OH. 25 It was also demonstrated that the OH(j=IOI)
other degrees of freedom.
cross sections increase with j. The combination of these two
Two simple reduced dimensionality potential energy sur-
effects results in OH rotational excitation, averaged over 0,
faces have been developed. They are based on a LEPS func-
tion to describe the reactive bonds and an accurate potential
for H20. The reduced dimensionality potentials have correct
TABLE V. Ground state tunneling and transmission coefficients on RDPI
reactant and product energies and incorporate the zero point
and RDP2.
energy of all modes not treated explicitly in the scattering
calculations. The transition state geometries are in reasonable RDPI RDP2
accord with ab initio calculations. One of the surfaces has a
vibrationally adiabatic ground state barrier height agreeing
T (K) rf KG rf KG

with ab initio data. 178 1165 758 2925 1932

It was found that the OH(j =0, 1) +CH4(v =0) 216 229 149 448 297
223 182 119 345 229
-+H 20+CH3 reactions mainly produce H20 in its vibrational 250 87 57 148 99
ground state. For reaction out of OH(j =0)+CH4 (v = 1), H20 273 53 35 84 56
is formed mainly with one quantum of energy in the local 300 34 22 50 33
vibrational stretch. The local stretch is essentially a superpo- 400 11 7.5 15 9.8
sition of the symmetric and asymmetric normal mode 600 4.5 2.9 5.1 3.4
800 3.0 1.8 3.2 2.1
stretches, wherefore these calculations predict that experi- 1000 2.4 1.4 2.5 1.6
mentally, excitation of these two modes should be observed. 1500 1.8 0.99 1.9 1.1
Corresponding observations were previously made for the

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J. Chern. contentVol.
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 5770 G. Nyman and D. C. Clary: CH 4 +OH-tCH3 +H 20 reaction

0'.7

0.6

:>. 0.5
-I-l
'M
rl
'M
.Q
cO 0.4
.Q
0
J..I
0..
t:::
0 0.3
'M
-I-l
U
cO
Q)
p:;
0.2

0.1

FIG. II. Reaction probability vs total angular momentum on RDPI for CHiv =0) +OH(j =0)-tCH 3+ H20 summed over all product states, Total energies (in
electron volts) are indicated and equally spaced.

lowering the reaction cross sections. The increase in the
j =Inl cross sections is probably due to the fairly large acti-
vation energy for the OH +CH4 reaction, whereby the in-
crease in total energy with increased j enhances reaction.
Thermal rate constants were calculated for the OH +CH4
reaction and were found to be in good agreement with ex-
perimental results. In particular, the experimentally observed
temperature dependence of the rate constant is well repro-
duced. There is also quite good agreement with a previous
VTST calculation. 14 Tunneling was found to dominate the
rate constant at room temperature.
It would be highly desirable to have a more accurate
potential energy surface in the transition state region, in par-
ticular, in regards to the shape of the barrier. Such informa-
tion can, however, not be expected to be easily obtained for
large polyatomic reactions. Our findings suggest that the ap-
proach described here is a practical and realistic way of
studying chemical reaction dynamics of polyatomic mol-
ecules.
ACKNOWLEDGMENTS
This research was supported by the Science and Engi-
neering Research Council. GN is grateful to the Swedish
Institute for financial support. DCC acknowledges a Royal
Society-Israel Academy Visiting Professorship at the Fritz
Haber Research Center, Hebrew University, Jerusalem,
where part of this paper was written. He would also like to
acknowledge the warm hospitality of Professor R. D. Levine.
The calculations were carried out on a Convex C2 computer
at Cambridge University.
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