Modeling The Kinetics of Bimolecular Reactions
Modeling The Kinetics of Bimolecular Reactions
Modeling The Kinetics of Bimolecular Reactions
4518
Donald G. Truhlar*
Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431
Received October 3, 2005
Contents
1. Introduction
2. Gas-Phase Thermal Reactions
2.1. Thermodynamics: Enthalpies and Free
Energies of Reaction
2.2. Kinetics
2.2.1. Arrhenius Parameters and Free Energy of
Activation
2.2.2. Collision Theory
2.3. Saddle Points and Potential Energy Surfaces
2.4. Rate Theory for Simple Barrier Reactions
2.4.1. Conventional Transition State Theory
2.4.2. Variational Transition State Theory
2.4.3. Anharmonicity
2.4.4. Tunneling, Recrossing, and the
Transmission Coefficient
2.4.5. Improvements in VTST Methodology
2.4.6. Reduced-Dimensionality Theory
2.4.7. Direct Dynamics Calculations
2.4.8. Fully Quantal Calculations
2.5. Bimolecular Reactions over Potential Wells
2.5.1. RRKM Assumption
2.5.2. Variational Transition State Theory for
Barrierless Addition Reactions
2.5.3. Master Equation and Its Application to
Reactions over Potential Wells
2.5.4. Energy Transfer
2.5.5. Solving the Master Equation
3. Gas-Phase State-Selected Reactions and
Product State Distributions
3.1. Electronically Adiabatic Reactions
3.2. Electronically Nonadiabatic Reactions
4. Condensed-Phase Bimolecular Reactions
4.1. Reactions in Liquids
4.2. Reactions on Surfaces and in Solids
4.3. Tunneling at Low Temperature
5. Concluding Remarks
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4546
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4553
4554
4556
4562
4563
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4568
4568
4570
4571
4572
6. Glossary of Acronyms
7. Acknowledgments
8. References
4572
4572
4572
1. Introduction
This review is concerned with the theoretical and computational modeling of bimolecular reactions, especially with
generally applicable methods for kinetics (i.e., overall rates
as opposed to detailed dynamics). It includes a basic
theoretical framework that can be used for gas-phase thermal
reactions, gas-phase microcanonical and state-selected reactions, and condensed-phase chemical reactions. The treatment
of gas-phase thermal reactions includes separate discussions
of simple direct reactions over a barrier, which usually have
tight transition states and reactions proceeding over a
chemical potential well, which can have a number of
additional complications, such as barrierless addition potentials (which generally have loose, flexible transition states),
competitive reaction pathways, isomerizations between multiple wells, and pressure-dependent energy transfer processes.
The section on thermal reactions has a heavy emphasis on
(generalized) transition state theory (TST) including multidimensional tunneling because this theory provides the best
available method to calculate thermal rate constants for all
but the very simplest systems. The section on state-selective
reactions and product state distributions includes an introduction to the theory of electronically nonadiabatic reactions
and coupled potential energy surfaces, as required for
modeling photochemical and chemiluminescent reactions.
The section on bimolecular reactions in liquid solution
considers diffusion control and equilibrium and nonequilibrium solvation.
A + B a C1 + + Cn
(2.1.1)
d[A]
dt
) k[A][B] - k[Ci]
(2.1.2)
i)1
where k and k are the forward and reverse temperaturedependent rate constants (or rate coefficients), respectively.
The equilibrium constant, K, for the process is given by the
quotient of the forward and reverse rate constants,1 and the
reaction quotient is defined by
K ) QoK(T) exp[-GoT/RT]
QK )
G ) RT ln
i)1
(2.1.5)
[Ci]
(2.1.4)
QK
K
(2.1.6)
(2.1.3)
[A][B]
Fernandez-Ramos et al.
2.2. Kinetics
2.2.1. Arrhenius Parameters and Free Energy of
Activation
From a phenomenological point of view, numerous
experiments have shown that the variation of the rate constant
with temperature can be described by the Arrhenius equation5
k ) A exp(-Ea/RT)
(2.2.1)
k(T) )
1
(T)Ko exp(-G,o
T /RT)
h
(2.2.2)
where G,o
is the quasithermodynamic free energy of
T
activation, and (T) is a transmission coefficient, Ko is the
reciprocal of the standard state concentration, h is Plancks
constant, and is 1/kBT, where kB is Boltzmanns constant.
(Note that some formulations include a symmetry number
that counts equivalent paths to the transition state; however,
we omit this and include symmetry numbers in G,o
T ,
which is equivalent8,9 and allows symmetry effects to be
included by the same methods that are well established for
real equilibria.) It is common practice, especially for reaction
kinetics in the liquid phase, to write eq 2.2.2 as
k(T) )
1 o
K exp(-Goact(T)/RT)
h
- RT ln (T)
(2.2.4)
kij(VR) ) VRij(VR)
(2.2.5)
1/2
(2.2.7)
where
Erel ) VR2/2
(2.2.8)
kij )
where
is the phenomenological free energy of
activation. Clearly
G,o
T
0 dErelErelr(Erel) exp(-Erel)
8
(
)
k)
(2.2.3)
Goact(T)
Goact(T)
(2.2.6)
i,j
8
(
)
0 Erelij(Erel) exp(-Erel)dErel
1/2
(2.2.9)
Sometimes it is also useful to define the reaction probability PR as a function of the impact parameter b, which is
defined as the distance of closest approach between the two
molecules in the absence of interparticle forces. The probability of reaction decreases to zero for large b. Actually,
we can consider a value of b ) bmax after which the reaction
probability is negligible, and the reaction cross section is
given by
r ) 20
bmax
PR(b)bdb
(2.2.10)
k(T) )
8
(
)
1/2
d2
(2.2.11)
V
hR )
8
(
)
1/2
(2.2.12)
k)V
h Rd2
(2.2.13)
Eo e Erel(1 - b2/d2)
Then the reaction cross section is
(2.2.14)
Fernandez-Ramos et al.
(2.2.15)
) b*2 )
8 1/2
exp(-Eo)
( )
k(T) ) d2
(2.2.16)
Veff ) -
1 Rq
L
+
2 r4
2r2
2
Veff(r) ) -
1 Rq2
b2
+ Erel
4
2 r
r
()
(2.2.18)
r* )
( )
1 Rq2
b Erel
1/2
(2.2.19)
Veff,* )
Erel2b4
2Rq2
(2.2.20)
b* ) (2Rq2/Erel)1/4
and the reaction cross section is
(2.2.21)
1/2
(2.2.22)
kL ) 2
( )
Rq2
1/2
(2.2.23)
r ) max
(2.2.17)
( )
2Rq2
Erel
(2Rq2/Erel)1/2
d2
(2.2.24)
kGorin(T) )
x2 (32)(C )
11/6
1/3
(kBT)1/6 (2.2.25)
nuclear coordinates of the system. According to the BornOppenheimer approximation,58-62 it is equal to the adiabatic
electronic energy, including nuclear repulsion. The electronically adiabatic energy E of the system is given by
E ) TR + VNR(R) + E(el)
(R)
(2.3.1)
(2.3.2)
Fernandez-Ramos et al.
Table 1. Electronic Structure Calculations of the Bond Lengths
(), Bond Angle (deg), and Barrier Height (kcal/mol) of the
Saddle Point of the F + H2 f HF + F Reaction
V
method
F-H
H-H
F-H-H
nonrel
rel
SEC
MR-CISD
MCG3a
MRCC
FN-DQMC
r12-ACPF-2
1.61-1.64
1.55
1.51
1.54
1.53
1.53
0.74-0.76
0.77
0.775
0.77
0.77
0.77
104-130
119
128
118
118
117
1.0-1.3
1.5
2.8
1.5
1.4
1.4
1.4-1.7
1.9
3.2
1.9
1.8
1.8
Version 2s.
they are not systematically improvable, although the predictions of DFT can be systematically improved by combining
them with successively higher levels of MCCMs.140 Furthermore, over time the density functionals have been
improved by better parametrizations.
Because the stationary points are often used to characterize the general features of a PES, algorithms for optimizing
stationary points are very important. These have recently
been reviewed.141 Methods for finding reaction paths are also
important, and the most commonly used methods require that
one first find a saddle point. More recently, nudged elastic
band methods have been developed that can compute a
reaction path without first finding a saddle point.142-146
Almost all density functionals involve some empirical
elements and should not be called ab initio; some workers
call them first principles methods, although the precise
boundary between first principles and other principles is not
clear.
In summary, a wide variety of quantum chemical methods
can allow us to obtain potential energy surfaces with high
accuracy, the limitation being the size of the system, although
the DFT-type methods can be applied to fairly big systems.
Trajectory simulations require knowledge of the PES over
broad ranges of configuration space. More limited PES
information is generally required for TST calculations, but
the amount of required information does increase with the
sophistication of the TST method. Various methods have
been developed to obtain an accurate representation of the
computed PES with the least computational effort. Reviews
of PESs for reactive systems are available,147,148 but progress
since then is substantial.
In general, the first step is to locate all the stationary points
important for the reaction. A particular geometry is a
stationary point of the PES if the first derivatives of the
potential (gradient) with respect to all the nuclear coordinates
are zero
V(R)
)0
R
(2.3.3)
Fernandez-Ramos et al.
27.5
10.2
10.0
9.6
10.0
10.2
4.8
24.3
7.8
7.8
3.2
2.3
3.0
2.0
6.8
6.6
5.5
4.0
5.4
4.6
3.3
5.2
4.2
2.7
5.0
4.7
1.6
1.4
12.4
12.5
12.6
12.0
11.2
12.6
11.1
13.3
12.1
11.5
8.8
8.5
2.5
2.0
8.0
2.3
2.2
2.2
2.2
3.3
0.6
8.9
2.9
2.8
3.6
3.3
1.7
1.5
1.0
1.4
1.9
2.8
2.3
3.4
33.8
1.5
2.8
3.9
3.2
11.0
4.3
15.6
a
The mean unsigned error for atomization energies is on a per bond
basis. b The cost for each method is the computer time for a singlepoint gradient calculation at a generalized transition state of the OH+ CH3F SN2 reaction divided by the computer time for the same
calculation at the MP2/6-31G(d) level with the same computer program
and same computer, averaged over two computers (IBM Power4 and
SGI Itanium 2).
AE6a
EA13
BH6
HAT12
NS16
MP2/6-31G(d)
MP2/6-31+G(d)
MP2/6-31+G(d,p)
MP2/6-31+G(d,2p)
MP2/6-31++G(d,p)
MP2/6-311++G(d,p)
MP2/6-311++G(2df,2pd)
SAC-MP2/6-31G(d)
SAC-MP2/6-31+G(d,p)
SAC-MP2/6-31+G(d,2p)
B3LYP/6-31+G(d,p)
B3LYP/MG3S
M05-2X/6-31+G(d,p)
M05-2X/MG3S
-8.0
-8.2
-5.1
-4.3
-5.3
-5.0
-0.7
-1.0
-0.5
-0.3
-1.5
-0.6
-1.4
0.0
27.5
10.2
9.9
9.5
9.9
10.2
4.7
24.3
7.2
7.2
-2.5
-1.5
-0.1
0.5
6.8
6.6
5.5
4.0
5.4
4.6
3.3
5.2
4.2
2.7
-5.0
-4.7
-0.6
-0.4
12.0
12.1
12.6
12.0
11.2
12.6
11.1
11.5
12.1
11.5
-8.8
-8.5
1.1
1.2
-2.2
1.1
1.1
1.0
1.1
3.3
0.6
-3.6
0.3
0.3
-3.6
-3.3
-0.6
-0.8
a
The mean unsigned error for atomization energies is on a per bond
basis.
(2.3.4)
where Rij and R0ij are the internuclear distance and the
equilibrium internuclear distance, respectively, and ij is a
parameter related to the harmonic frequency, reduced
mass, and dissociation energy of the diatom. In the ROBO
method, as in the RMS method, the potential is written as a
sum of a radial function multiplied by an angular function
plus an interaction term. The LAGROBO functional is a
weighted sum of the ROBO functions for the different
rearrangement channels of the system (3 for a triatomic
system and 12 for a four-atom system). This method was
recently applied to the OH + HCl reaction.230 For systems
with more than four atoms, Garca et al.251 developed an
approximate method based partly on the LAGROBO method
and partly on the MBE method, which they applied to build
the PES for the hydrogen abstraction reaction from methane
by chlorine. Duin et al.295 proposed an extension of molecular
mechanics to reactive systems by using bond orders.
Related to the above methods is the reduced dimensionality (RD) approach developed by Clary and co-workers213,231,234,245,257 to study hydrogen abstraction reactions.
These reactions are all of the type D-H + A f D + H-A
(D and A are the donor and acceptor atoms, respectively,
and H is hydrogen) and the RD potential is constructed from
a sum of two 2D-Morse functions, which are given in
Fernandez-Ramos et al.
V ) p(x) + qi,j(x)yi,j
(2.3.5)
i<j
M1 M2
MN
i1 i2
iN
j)1
V ) Wi(R)Ti(R)
(2.3.7)
i)1
Wi(R) )
Vi(R)
N
(2.3.8)
Vj(R)
j)1
Vi )
1
|Z(R) - Z(Ri)|2p
(2.3.9)
V)
V11(R) V12(R)
V12(R) V22(R)
(2.3.10)
1
V(R) ) {(V11(R) + V22(R)) - [(V11(R) - V22(R))2 +
2
4V12(R)2]1/2} (2.3.11)
where V12(R) is called the resonance energy function or
resonance integral. An estimate of V12(R) is obtained from
the scheme proposed by Chang and Miller.306,307 In their
approach, the resonance integral is expressed as
gradients, and Hessians, and for a given point i the potentials are expanded in Taylors series V(R;i), V11(R;i), and
V22(R;i), to second order about the R(i) geometry. Each
Hessian generates a Taylors series of V12(R) about another
point. These series are joined by Shepard interpolation, and
the new resonance integral VS12(R), is given by
n
VS12(R) ) wi(R)V12(R;i)
(2.3.13)
i)1
(2.3.14)
V ) VAVB + VBN
(2.3.15)
Fernandez-Ramos et al.
used to treat molecular vibrations and vibrational spectroscopy, and the nonreactive subsystem is labeled B. If we use
a two-state valence model, eq 2.3.10 can be written as
V ) mineiv
VARR VARP
+ VBN
VARP VAPP
(2.3.16)
or
V ) mineiv
(2.3.17)
V ) mineiv
VAB
VARP
R
VARP VAB
R
(2.3.18)
quadratic terms in the multidimensional Gaussian are positive, whereas they assumed that they are all negative.
The MCMM method presented above also has the form
of eq 2.3.18, and it provides a systematic way to parametrize
the EVB method. The use of MM in this method helps in
two ways. First of all, it makes it possible to interpolate V12,
rather than V; V12 is much smoother. Second, the molecular
mechanics terms describe the variation of the potential as a
function of the spectator degrees of freedom quite well, and
so one does not need to add Hessian points with various
values of the spectator coordinates to incorporate that
variation. It is possible to save further computational expense
by using electronic structure theory to calculate partial
Hessians involving only the most critical degrees of freedom.241 Recently, the MCMM method has also been applied
to the barrierless BH5 dissociation reaction233 and to protontransfer reaction in the water trimer. 255
The MCMM method, although based completely on ab
initio electronic structure calculations, is not a straight directdynamics method because an algorithm for interpolation is
needed to calculate geometries that are not available in the
initial set of input data. An alternative approach that avoids
interpolation is the hybrid VB/MM method of Shurki and
Crown.314 This method combines molecular mechanics for
the diagonal elements with a standard ab initio valence
bond package for the off-diagonal elements, thereby avoiding
parametrization as well as interpolation. An empirical
combined valence bond molecular mechanics (CVBMM)
method has also been proposed.300 In this method, the VB
part is an extension of the semiempirical VB methods that
were originally developed for small systems.
As discussed above, another alternative is to avoid both
MM and interpolation and to use straight direct dynamics
to build the PES, that is, to calculate on the fly every
energy, gradient, or Hessian needed for the dynamics
calculation. Unfortunately, this cannot be done economically
if the level of ab initio theory employed includes much of
the electronic correlation and involves large basis sets. One
possibility is to use a neural network for function approximation; this combines243 electronic structure calculations with
sampling methods that make use of molecular dynamics
calculations to sample important parts of the PES in a similar
way to how they are used by Collins and co-workers218 for
Shepard interpolations.
Another possibility is to do high level ab initio calculations
at the stationary points (reactants, products, and transition
state) and try to find a lower-level method that provides
similar energies and geometries. Sometimes it is possible to
find a low-level ab initio method that fulfills the requirement;
however, if the system is relatively big even a low-level ab
initio method can be impractical. A common approach is to
use semiempirical molecular orbital theory instead of ab initio
or DFT methods.331,332 As mentioned in Section 2.1, some
of the integrals evaluated in the ab initio methods are replaced
by parameters in some of the semiempirical methods; in other
semiempirical methods, the parameters are scaling factors
or occur in additive terms. In any of these methods, the
parameters can be optimized in a general way against a broad
or representative database, or they can be modified to
reproduce the energetics, some frequencies (for instance the
imaginary frequency at the transition state), and/or some key
geometric parameters important for a specific reaction or
range of reactions. In general, these parameters are reaction
dependent, and therefore this produces a semiempirical
1 QC(T)
exp(-V)
k (T) )
h R(T)
(2.4.1)
k(T) )
1
K (T)
h
(2.4.2)
k(T) )
1 o
K exp[-G,o/RT]
h
(2.4.3)
k(T) )
Fernandez-Ramos et al.
1 o
K exp[S,o/R] exp[-H,o/RT] (2.4.4)
h
H,o ) Ea - 2RT
(2.4.5)
and343
A)
( )
Koe2
exp(S,o/R)
h
(2.4.6)
or
S,o ) R ln(hA/Ko) - 2R
(2.4.7)
where Ko is the reciprocal of the concentration that corresponds to a pressure of 1 atm at temperature T.
()
mi
Rj )
1/2
(2.4.9)
F
+ Fv ) 0
t
(2.4.10)
d6NF ) d6NFv
t
(2.4.11)
where
3N
d6N ) dpidRi
(2.4.12)
i)1
dNR
) d6NFv
dt
(2.4.13)
dNR
) SdsF(vn)
dt
(2.4.14)
F+ ) S dsF(vn)
(2.4.15)
(2.4.16)
pz
F(T)V
F(T)
)
V[A][B] NANB
(2.4.22)
(2.4.23)
GT
C (T,z*) )
exp[VRP(z ) z*)]
Vh
(3N-1)
d6N-2
dz pz
vn ) ) > 0
dt
kC(T) )
(2.4.17)
F ) F0 exp[-H]
(2.4.18)
kGT
C (T,z*) )
GT
1 C (T,z*)
exp[-VRP(z ) z*)] (2.4.25)
h A(T)B(T)
C
C
( )
h2
1
)
2
rel(T)
so that
NR ) F0d6N exp[-H]
(2.4.19)
F+ ) F0 d6N-2 exp[-HGT(u,pu; z )
pz
(2.4.26)
3/2
(2.4.27)
kGT
C (T,z*) )
1 QC (T,z*)
exp[-VRP(z ) z*)] (2.4.28)
h R(T)
C
where QGT
C is the partition function defined by
GT
GT
GT
C (T,z*) ) trans(T)QC (T,z*)
(2.4.29)
(2.4.30)
and
Fernandez-Ramos et al.
kGT
C (T,s)
GT
1 QC (T,s)
exp[-VMEP(s)]
)
h R(T)
(2.4.31)
dividing surface must separate the reactant region of configuration space or phase space from the product region. Then
the classical mechanical CVT rate constant is given by
kCVT
C (T)
GT
CVT
1 QC (T,s ) s* )
exp[-VMEP(sCVT
)
* )]
R
h
C(T)
(2.4.34)
kGT
C (T,s) )
K,o
exp[-GGT,o
C (T,s)/RT] (2.4.35)
h
[GGT,o
C (T,s)]|s)s*CVT ) 0
s
(2.4.36)
where s ) sCVT
is the optimized position of the dividing
*
surface. This condition is equivalent to
GT
[k (T,s)]|s)s*CVT ) 0
s C
(2.4.33)
dx
) -g
ds
(2.4.37)
L(x)F(x)L(x) ) (x)
(2.4.38)
( )
m(x)
m(x ) )
LGT(s)FP(s)LGT(s) ) (s)
1/2
, m ) 1, ..., 3N
(2.4.39)
(2.4.40)
m(s) )
(2.4.42)
( )
m(s)
1/2
, m ) 1, ..., 3N
(2.4.44)
g[x(sj-1)]
(2.4.41)
x(sj ) sj-1 ( s) ) x(sj-1) - s
|g[x(sj-1)]|
This algorithm requires quite small steps and therefore a large
number of potential energy gradient evaluations. This is not
a problem if the PES is given in analytical form, but it can
be very time-consuming for high-level direct dynamics.
Improvements to this method and other more efficient
methods that may use larger steps are described elsewhere.141,162,384-389 Some of these algorithms, such as the
Page-McIver method,384 make use of Hessians, F(s), along
the MEP.
To calculate the vibrational part of QGT
C (T,s) in eq 2.4.31
we need to obtain generalized normal-mode frequencies
along the reaction path. These are called generalized because
true normal-mode analysis is only defined at stationary points
and for systems that are not missing any degrees of freedom.
The elimination of the reaction coordinate is accomplished
by rotating the coordinate system369 or by a projection
operator;390 here we describe the latter method. It involves
diagonalizing the projected Hessian matrix, FP(s), which is
obtained from383,390
(2.4.43)
CVT/G(T) ) (T)kCVT(T)
(2.4.45)
kCVT(T) )
GT
CVT
1 Q (T,s ) s* )
exp[-VMEP(sCVT
* )]
h
R(T)
(2.4.46)
and
R(T) ) rel(T)QAel(T)QAvib(T)QArot(T)QBel(T)QBvib(T)QBrot(T)
(2.4.48)
where rel is the relative translational partition function per
unit volume given by eq 2.4.27 and Qel, Qvib, and Qrot are
the electronic, vibrational, and rotational partition functions,
respectively. Notice that we have now removed the subscripts
C, and all partition functions are now to be computed in
principle from quantized energy levels. In practice, it is
almost always a good approximation to still treat rotation as
classical, but quantization of vibrations is very important.
Fernandez-Ramos et al.
dGT
(s) exp{-[V(s) - VMEP(s)]}
QGT
el (T,s) )
)1
(2.4.49)
where
V(s) ) E(el)
(s) + VNR(s)
(2.4.50)
(2.4.51)
QGT
rot (T,s) )
(2.4.52)
p2rot
[( )
exp[-(1/2)pm(s)]
{1 - exp[pm(s)]}
1/2
/rot
(2.4.53)
GT
) Qvib,m
(T,s)
(2.4.54)
m)1
GT
(T,s) being the vibrational partition function of
with Qvib,m
mode m,
GT
GT
Qvib,m
(T,s) ) exp[-Evib,m
(nm,s)]
(2.4.55)
nm
1
pm(s)
2
(2.4.58)
EGint(s) )
GT
(nm ) 0,s)
Evib,m
(2.4.59)
m)1
(2.4.60)
(2.4.57)
m)1
2 3
IA(s)IB(s)IC(s)
p 2
QGT
vib (T,s)
GT
Qvib,m
(T,s) )
F-1
2I(s)
QGT
rot (T,s) )
dXk e-Eint,k
(2.4.56)
wXk
QXint(T)
(2.4.61)
(2.4.62)
k(T) )
1
hR(T)
(2J + 1)
J
ijlml
J
P (E)
0 ijlml
exp(-E)dE
(2.4.64)
(2.4.65)
J
is the reaction probability as a function of the
and Pijlm
l
rotational and vibrational quantum numbers of reactants and
also l, ml, and total angular momentum J. The factor of 2J
+ 1 results from a sum over 2J + 1 values of MJ, the
component of J on an arbitrary space-fixed axis, since the
probabilities are independent of MJ. Let R denote the
collective set of quantum numbers ijlml. Then J, MJ, and R
represent a channel specified by a complete set of quantum
numbers labeling the initial state of a collision.
Next define the J-resolved cumulative reaction probability
NJ(E) as393-396
NJ(E) )
J
(E) ) PJR(E)
Pijlm
ijlml
1
hR(T)
N(E) ) NGT
vr (E,s)
NVT(E) ) minNGT
vr (E,s)
NGT
vr (E,s)
s
(2.4.67)
(2.4.68)
J MJ R
(2.4.75)
s)s*VT(E)
)0
(2.4.76)
NGT
vr (E,s) ) [E - VMEP(s) n
1
N(E) exp(-E)dE (2.4.70)
hR(T) 0
(2.4.74)
or equivalently
kVT(T) )
J
is the energy
where is the Heaviside function, and ERJM
1
0N(E) exp(-E)dE
R
h (T)
(2.4.73)
J MJ R
J
N(E) ) (E - EJM
R )
(2.4.66)
k(T) )
k(T) )
(2.4.72)
J MJ R
i,j
(2.4.71)
GT
GT
EGT
vib (n,s)]Nrot [E - VMEP(s) - Evib (n,s),s] (2.4.77)
383
where for NGT
rot (E,s) we use the classical approximation.
CVT
If we calculate NGT
(E,
s
)
s
)
we
obtain
the
CVT
vr
*
thermal rate constant. Another possibility is to optimize the
generalized transition state microcanonically for energies up
to the microcanonical variational threshold energy and
canonically for higher-energy contributions. This leads to
the improved canonical variational theory (ICVT),383,400
which has the same threshold as VT but the calculations
are almost as simple as for CVT. One can easily show that
(2.4.78)
Fernandez-Ramos et al.
(2.4.79)
2.4.3. Anharmonicity
Conventionally, one would compute the reactant partition
function accurately by a sum over states, although in practice
this has only recently become possible for molecules with
more than 3-4 atoms.422 An alternative method to compute
accurate vibrational-rotational partition functions is the
V(m)[s,um(s)] ) (1/2)kmm(s)[um(s)]2
(2.4.80)
where kmm is the principal (the two subscripts are the same)
normal-coordinate force constant, and um(s) is the normalmode coordinate for a geometry x close to x(s), specifically,
um(s) ) [x - x(s)]LGT
m (s)
(2.4.81)
2.4.3.1. Principal Anharmonicity. In general the vibrational degrees of freedom of the stationary points and
generalized transition states along the path are bound by an
anharmonic potential:
1
V(m)[s,um(s)] ) kmm(s)[um(s)]2 + kmmm(s)[um(s)]3 +
2
kmmmm(s)[um(s)]4 + (2.4.82)
where kmmm(s) and kmmmm(s) are the third and fourth principal
normal mode force constants. These force constants can be
obtained from numerical derivatives of analytic gradients.383
One difficulty with using this expansion is that the cubic
term is always unbounded from below, and the quartic term
is unbounded from below if kmmmm is negative. It therefore
requires finesse to include anharmonicity in a practical
scheme.
One approach commonly used to treat anharmonicity is
to assume that the normal modes are independent (not
coupled), so the partition function may still be evaluated by
eq 2.4.54. This section begins with independent normal-mode
(INM) methods, and within the INM framework we discuss
Morse and quartic anharmonicity,360 together with the
Wentzel-Brillouin-Kramers (WKB) method425-427 and the
anharmonicity of bond torsional modes.
To evaluate the energy levels of the 1D potential (2.4.82)
one possibility is to replace that potential by a Morse
function:428
2
(2.4.83)
V(m)[s,um(s)] = De(s){exp[-(m)
M (s)um(s)] - 1}
De ) D - VMEP(s)
(2.4.84)
(2.4.85)
(m)
M are chosen this way is known as Morse approximation
I.360,365,429 The energy levels of this potential are given by428
GT
Evib,m
(n,s) ) pm(s)(nm + 1/2)[1 - x(m)
M (s)(nm + 1/2)]
(2.4.86)
x(m)
M (s) ) pm(s)/4De(s)
(2.4.87)
This Morse model does not give any improvement for modes
in which kmmm(s) ) 0, such as the bending modes of linear
systems, out-of-plane modes of planar systems, and certain
stretching motions. This kind of mode can be treated by a
quadratic-quartic model with
1
V(m)[s,um(s)] = kmm(s)[um(s)]2 + kmmmm(s)[um(s)]4
2
(2.4.88)
which can sometimes be accurately approximated by a
perturbation-variation method to obtain the energy levels.430,431 A centrifugal oscillator treatment provides a more
accurate approximation.432 Anharmonicity of bending modes
is often dominated by quartic anharmonicity, and it can be
very significant, especially at high temperature.431
The anharmonicity can be also treated by the WKB
approximation.425-427 Since this method is more expensive,
it might be used only for finding the zero-point energy of
some or all the normal modes. For several atom-diatom
reactions, the results obtained by VTST improve if the WKB
method is used to treat anharmonicity instead of the Morse
model.427
Another important source of error in calculating vibrational
partition functions is the inapplicability of the harmonic
oscillator (HO) approximation for low-frequency torsional
modes. Such modes show a hindered rotation transition from
HO behavior at low temperature to free internal rotation at
high temperature. An interpolatory function that is reasonably
accurate has the form433
HO
QHR
m Qm f m
(2.4.89)
where QHR
m is the approximate hindered-rotor (HR) partition
function, QHO
m is the harmonic oscillator partition function,
and fm is an interpolating function given by
fm ) tanh QFR
m wm
(2.4.90)
Fernandez-Ramos et al.
V ) Ve +
m2um2 + VAnh
(2.4.91)
m)1
Qvib )
exp(-E0)
F
(2.4.92)
[1 - exp(-m)]
m)1
(T) ) g(T)(T)(T)
(2.4.93)
k (T) )
US
QGT
el (T)
R
h (T)
0NUS
vr (E) exp(-E)dE
(2.4.94)
where
US
VT
NUS
vr (E) ) Nvr (E) (E)
(2.4.95)
US(E) ) 1 +
NvrVT(E)
Nmin
vr (E)
NVT
vr (E)
Nmax
vr (E)
Fernandez-Ramos et al.
(2.4.96)
GT
where Nmin
vr (E) is the second lowest minimum of Nvr (E, s)
max
GT
and Nvr (E) is the maximum of Nvr (E, s) that lies between
the two minima. It should be noticed that the US calculation
is nonvariational, although it always satisfies that kUS(T) e
kVT(T). The same analysis can be applied to a canonical
ensemble by defining canonical probabilities in terms of
canonical-ensemble averages of the flux through these
surfaces.494 The resulting canonical unified statistical (CUS)
thermal rate constant assumes the form
kCUS(T) ) kCVT(T)CUS(T)
(2.4.97)
When there are both consecutive and competitive dynamical bottlenecks, one may use the competitive canonical
unified statistical (CCUS) model.413,500,501
Whereas the US and CUS models involve statistical
estimates of recrossing probabilities, it is also possible to
use trajectories for this purpose. Keck502,503 and Anderson504-506
showed how trajectories can be used to calculate a correction
for the breakdown of the TST assumption in a classical
mechanical context. In fact, this is a convenient way to do
trajectory calculations for gas-phase reaction processes
kX/Y(T) ) X/Y(T)kX(T)
(2.4.98)
k/Y(T) ) /Y(T)k(T)
(2.4.99)
,W(T) ) 1 +
1
|p|2
24
(2.4.100)
(2.4.101)
GT
GT
EGT
int (n,J,s) ) Evib (n,s) + Erot (J,s)
(2.4.102)
where
which is given by eq 2.4.58. A justification for this groundstate approximation is postponed until Section 3.1. The
ground-state transmission coefficient is given by the ratio
of the thermally averaged ground-state quantal transmission
probability PG(E) to the thermally averaged ground-state
transmission probability evaluated with the assumption of
classical reaction coordinate motion, PGC (E):401,491
0PG(E) exp(-E)dE
(T) )
0 PGC(E) exp(-E)dE
X/G
(2.4.103)
(T)]}
PGC (E) ) {E - VGa [sCVT
*
(2.4.104)
E < E0
0,
-1 E e E e VAG
{1 + exp[2(E)]}
0
PSAG(E) )
AG
AG
1 - PSAG(2VAG - E) V e E e 2V - E0
AG
1,
2V - E0 < E
(2.4.111)
where
(2.4.105)
For the ICVT and VT the classical transmission probability
is383
(2.4.106)
exp{VGa [sCVT
* (T)]}
VT/G(T) ) CVT/G(T)
exp(-VAG)
(2.4.107)
PSAG(E) ) {1 + exp[2(E)]}-1
E0 ) max
(2.4.108)
VGa (s ) - )
VGa (s ) + )
(s) ) d2x/ds2
(2.4.112)
(2.4.113)
) cos-1
mAmC
(2.4.114)
[- (s)ds]
+
dxR
dxP dxR dxR
)
) - (1 + cos )
ds
ds
ds ds
(2.4.115)
Fernandez-Ramos et al.
(s) ) min
m)1
am(s) ) - m(s)tm(s)
(2.4.117)
(2.4.118)
where s0 < 0 is the classical turning points of the reactioncoordinate motion on the reactant side. In the next stage of
the collisions tunneling is assumed to occur, without assuming vibrational adiabaticity, along the reaction path and along
straight-line paths that connect the reactants valley turning
point to a products valley turning point. Specifically, the
linear paths connect the point s0 on the reactant side to a
point (s1 > 0) with an identical value of eq 2.4.118 on the
product side.
The primitive tunneling amplitude Ttun(s0) along the
straight tunneling path initiating at s0 is approximated
semiclassically as
Ttun(s0) ) exp[-(s0)]
(2.4.119)
POMT(E) ) max
PLCT(E)
PSCT(E)
(2.4.120)
Cl + HBr a ClH + Br
was carried out by Lim and Truhlar.544 Those authors found
out that nonequilibrium effects for this reaction are negligible
when product concentrations are negligible. This conforms
) - RT ln
Gsub(T) ) VMEP(sCVT
*
QCVT(T)
R(T)K,o
(2.4.121)
Gnonsub
(T) ) -RT ln (T)
(2.4.122)
Fernandez-Ramos et al.
GOGT,0(T) ) maxGGT,0(T,n )
n
(2.4.123)
( )
s - s0
2
z ) arctan
(2.4.124)
OMT
reaction
OH + CH3CH2F f CH3CHF + H2O
H + SiCl4 f SiCl3 +HCl
H + C2H4 f C2H5
H + C2H5SiH2 f C2H5SiH + H
H + NF3 f NF2 + HF
H + (CH3)3GeH f (CH3)2Ge + H2
H + (CH3)3GeD f (CH3)2Ge + HD
H + (CH3CH2)2SiH2 f (CH3CH2)2SiH + H2
O + CH3CHF2 f CH3CF2 + OH
Cl + CH3Cl f CH2Cl + HCl
Cl + C2H5Cl f CH3CHCl + HCl
Cl- + CH3f ClCH3 + ClCl- + CH3Br f ClCH3 + BrOH + HCl f C1 + H2O
OH + D2O f OD + HDO
OH + CD4 f CD3 + HDO
OH + 13CH4 f 13CH3 + H2O
OH + CH3Cl f CH2Cl + H2O
OH + CH3SH f CH3S + H2O
OH + CH3OCl f CH2OCl + H2O
OH + CH3C(O)CH3 f (CH3)2C(O)OH
OH + (CH3)2SiH2 f (CH3)2SiH + H2O
OH + HOCH2C(O)H f HOCH2CO + H2O
OH + (cyclo-C3H5)CH(CH3)2 f
(cyclo-C3H5)C(CH3)2 + H2O
HF + H2SiLiF f H3SiF + LiF
C2H + H2 f H + C2H2
NO2 + CH2O f CHO + HONO
CH3 + H2 f H + CH4
CH3 + CH2O f CHO + CH4
CH3 + (CH3)2O f CH3OCH2 + CH4
CH3 + C2H5OH f CH3CHOH + CH4
CH3Cl(H2O) + NH3(H2O) f
(CH3NH3+)(Cl-)(H2O)2
C6H5 + (CH3)2CO f CH3C(O)CH2 + C6H6
H + H2S f HS + H2
H + CH4 f CH3 + H2
H + CH3OH f CH2OH + H2
H + N2H4 f H2NNH + H2
O + CD4 f CD3 + OD
F + CH4 f CH3 + HF
Cl + 13CH4 f 13CH3 + HCl
Cl + C2H6 f C2H5 + HCl
OH + H2 f H + H2O
OH + NH3 f NH2 + H2O
OH + CH3F f CH2F + H2O
OH + CH2F2 f CHF2 + H2O
OH + CF3CH3 f CF3CH2 + H2O
OH + C3H8 f (CH3)2CH + H2O
OH + CHF3 f CF3 + H2O
OH + C8H18 f C8H17 + H2O
HBr + HCCH f H2CCHBr
C2H + H2 f C2H2 + H
CH2Cl + CH3F f CH2F + CH3Cl
FO-(H2O) + C2H5Cl f
C2H4 + HOF(H2O) + ClCF3 + CD3H f CD3 + CHF3
CF3 + C2H6 f C2H5 + CHF3
CF3 + C3H8 f (CH3)2CH + CHF3
C2H4 + C4H6 f C6H10
N2O5 + H2O f 2HNO3
OH + CHF3 f CF3 + H2O
ref
603
622
612
633
616
626
625
636
638
647
649
164
600
602
610
628
642
647
631
644
627
645
640, 643
648
646
614
629
162
635
630
639
605
632
615
624
611
549
607
641a
606
403
623a
601
608
621
618
212
619
613
604
614
210
609
522, 524, 551
524
524
620
634
650
CO2 reaction.665 Therefore, the calculation of rate constants from the cumulative reaction probability or the flux
autocorrelation functions is preferred for larger systems.54,56,57,659,662-664,666-671
The time correlation function approach is well suited not
only to gas-phase reactions54-57,652,654,655,658,666-671 but also
Fernandez-Ramos et al.
The first step to treating a multiple-well, multiplearrangement reaction theoretically is to treat the component elementary steps individually. Transition-state theory
is used to calculate the rate coefficients for these steps.
This must be done at the microcanonical or microcanonical/J-resolved level, where J is the total angular momentum
quantum number. A microcanonical/J-resolved ensemble
takes explicit account of the dependence of reaction rates
on total energy or total energy and total angular momentum. These transformations from one arrangement to
another are, broadly speaking, of two types: those where
there is an intrinsic barrier between the configurations and
those where there is not; both possibilities are indicated in
the diagrams of Figure 5. By the term intrinsic barrier, we
mean a potential energy barrier in the exoergic direction.
For isomerizations that have a barrier and for fragmentation
of a complex to a radical plus a molecule in which the reverse
association has a barrier, the transition-state theory methods
discussed above can be used directly. For fragmentation to
a pair of radicals in which the reverse association has no
barrier, special methods are required. We describe these
methods below. But first we consider the basic assumption
that holds the multiple-well, multiple arrangement theory
together.
The fundamental idea that underlies this theory is known
as the RRKM assumption or the strong-coupling approximation. This is an assumption about the nature of the dynamics
of the collision complexes while they are in the well regions
of the potential. It is most easily described and understood
from a classical (rather than quantum) perspective, although
it may be more valid in a quantum-mechanical system than
in a classical one. The RRKM assumption says that the
degrees of freedom of a highly excited, isolated molecule
or collision complex are so strongly coupled that, no matter
how localized in phase space an ensemble of such complexes
is prepared, the ensemble will evolve to fill the entire phase
space available to it uniformly (consistent with conservation
of energy and angular momentum) on a time scale much
smaller than the characteristic time for reaction (i.e., for an
elementary step). Each step thus takes place exclusively from
a microcanonical/fixed-J ensemble (frequently approximated
simply by a microcanonical ensemble). This is illustrated
schematically in Figure 6. The isolated pockets of complexes
on the left of the figure might correspond to depositing
energy in a particular bond or normal mode of the molecule,
or they might correspond to isolating the complexes near a
transition-state dividing surface through which they were
formed. The subsequent trajectories of the complexes are
Q(T) ) Qconserved
(T)Qtransitional
(T)
(2.5.1)
Fernandez-Ramos et al.
N(E,J) ) 0 dNtransitional
(,J)Fconserved
(E - ) (2.5.2)
E
k(E) )
N(E)
(2.5.3)
hR(E)
R
k(E) )
N(E)
hFR(E)
(2.5.4)
k(E,J) )
N(E,J)
hR(E,J)
(2.5.5)
and
k(E,J) )
N(E,J)
hFR(E,J)
(2.5.6)
Veff(R) ) V(R) +
p2l(l + 1)
2R2
(2.5.7)
(E,J) ) (J,j,l)(j,j1,j2)
Ntransitional
PST
j1 j2 k1 k2
1
d12d1d2dp12dp1dp2
hn
exp{- [K + V(12,1,2,r)]/kBT} (2.5.9)
Qtransitional(T,R) )
Qtransitional(T,R) ) Qrot1Qrot2
2R2kBT
p2
exp(-V(12,1,2,r))12,1,2 (2.5.10)
Q(T,s) )
dRdp
exp[-(K + V)](S - s)S (S )
hn
(2.5.11)
Fernandez-Ramos et al.
Qtransitional(T,s) ) 2
( )( )
kBT
p2
s2
{ 2I(k)
i }
2 k)1 i)1
exp(-V(12,1,2)) (2.5.12)
2 (k)
1 + (n(12) d(k)n(k)
i ) /Ii
(2.5.13)
k)1i)1
where n(12) is the unit vector pointing from the second pivot
point to the first one, and n(k)
i is the unit vector directed
along the principal axis i of the fragment k. Again, similar
expressions involving powers in (E - V) or (E - V - Erot)
have been obtained for the microcanonical and microcanonical/J-resolved cases.759-765
The kinematic factor is unity for center-of-mass pivot
points and is otherwise greater than unity. This implies that
any reduction in the predicted rate coefficient due to variation
in the form of the reaction coordinate is due entirely to
increased potential values in the Boltzmann orientational
average. Empirically, the optimal dividing surfaces have been
found to have a shape that follows the potential energy
contours for small angular deviations from the minimum
energy path while sampling the highly repulsive interactions
at large deviations.766-768 In many instances, the optimal
dividing surfaces are obtained by placing the pivot points
near the center of the radical orbitals. For a variety of atomplus-radical reactions, the contours of the radical orbitals
were found to be a good approximation to the optimized
dividing-surface shape.766-768 Indeed, using the radical-orbital
contours as a dividing surface might well provide an even
more optimal transition-state theory estimate.
The most difficult aspect of the implementation of VRCTST involves the generation of a suitable potential energy
surface. This potential energy surface generally must span
the region from 2 to 4 in the incipient bond distance and
cover all orientations of the two fragments. Early work
employed qualitative model surfaces based, for example, on
assumed extrapolations and interpolations of the potential
from the molecular bonding to the long-range interaction
regions.769-771 Such model studies are similar to empirical
implementations of the statistical-adiabatic-channel model727,728
and to other models assuming an exponential dependence
of transitional mode frequencies on the reaction coordinate.772
For radical-radical reactions, considerable effort has
recently been devoted to obtaining accurate potential energy
surfaces from detailed electronic structure calculations. A
difficulty is that accurate calculations of potential energy
curves for radical-radical reactions generally must involve
multireference wave functions;773-775 standard single-reference-based methods are generally inadequate in the transition-state region for this kind of reaction. When one of
the fragments is an atom and the other is nonlinear, the
requisite potential energy surface is 3D. In this instance,
dni
dt
) (pijnj(t) - pjini(t))
j
(2.5.14)
nB . nX . nR
(2.5.15)
dni(E,J)
dt
Fernandez-Ramos et al.
j*i
j*i
Np
Keqikdi(E,J)Fi(E,J)nRnX -
kp (E,J)ni(E,J), i ) I,...,M
p)1
(2.5.16)
dnR
dt
) E(i)kdi(E)ni(E)dE i)I
Fi(E,J) ) Fi(E,J)e-E/Qi(T)
(2.5.17)
dni(E)
dt
) ZE(i)Pi(E,E)ni(E)dE - Zni(E)
0
j*i
j*i
Np
kp (E)ni(E), i ) I,...,M
p)1
(2.5.18)
The term in eq 2.5.16 involving Fi(E,J) (or that involving Fi(E) in eq 2.5.18) is more naturally written as
kai(E,J)nRnXFR,X(E,J)e-E/QR,X, where kai(E,J) is the association rate coefficient for formation of isomer i from the
reactants, QR,X is the partition function per unit volume of
reactants (including relative translational motion), and
FR,X(E,J) is the corresponding density of states. The form
used in eq 2.5.16 comes from applying microscopic reversibility to the association/dissociation reactions; both forms
assume that the reactants are maintained in thermal equilibrium. The form shown in the equation has the advantage
that is does not require the explicit calculation of FR,X(E,J),
which is a complicated convolution of the state densities of
the two fragments R and X. Nevertheless, we have use for
both formulations below.
nRnXKeqiE(i)kdi(E)Fi(E)dE (2.5.19)
i)I
bmax2 E ) 0
bmax
Eb 2bdb
(2.5.20)
P(E,E) )
1
exp(-E/R), E e E
CN(E)
(2.5.21)
P(E,E) )
1
[(1 - f) exp(-E/R1) +
CN(E)
f exp(-E/R2)] E eE (2.5.22)
P(E,E) )
E Y
1
exp R
CN(E)
[ ( )]
E e E (2.5.23)
Fernandez-Ramos et al.
|n(E,J) ) K-1(E,J)|b(E,J)nRnXFR,X(E,J)e-E/QR,X(T)
(2.5.25)
where K-1(E,J) is the inverse matrix of K(E,J). The rate of
formation of bimolecular products can also be described by
a vector equation,
d|n(E,J)
) -K(E,J)|n(E,J) +
dt
nRnX|b(E,J)FR,X(E,J)e-E/QR,X (2.5.24)
where |n(E,J) is (in Dirac notation) the vector of population
densities for a given E and J, i.e., each component of the
vector corresponds to the population of a different well, and
d|P(E,J)
) D(E,J)|n(E,J)
dt
(2.5.26)
d|P(E,J)
)
dt
D(E,J)K-1(E,J)|b(E,J)nRnXFR,X(E,J)e-E/QR,X(T)
(2.5.27)
Integrating over E and summing over J, one can easily
identify a vector of thermal rate coefficients as the factor
multiplying nRnX,
|k0(T) )
1
QR,X(T)
(2J +
J
-1
|k0(T) )
1
hQR,X(T)
(2J +
J
NH2 + NO f N2 + H2O
(R1a)
NH2 + NO f NNH + OH
(R1b)
NH2 + NO f N2O + H2
(R1c)
Figure 10. Plot of the total rate coefficient for the NH2 + NO
reaction versus temperature. Symbols denote various experimental
measurements, whereas the solid line denotes collisionless-limit
master-equation predictions.
Fernandez-Ramos et al.
d|w(t)
) G|w(t)
dt
(2.5.30)
(I)
|w(t) ) yI(E(I)
O ),...,yI(El),...,yi(E0 ),...,yi(El),...,
nX
QR,XE
1/2
XR,...
(2.5.31)
G|gj ) j|gj
(2.5.32)
One can then expand |w(t) in this basis and obtain the
solution of eq 2.5.30 in the form
|w(t) ) T |w(0)
(2.5.33)
T ) ejt|gjgj|
(2.5.34)
j)0
N ) Ni + Np + 1
(2.5.35)
i)1
Xi(t) ) E(0)xi(E,t)dE
Nchem ) S - 1
(2.5.36)
(2.5.37)
Nk )
S-1
S(S - 1)
n)1
n )
(2.5.38)
Xi(t) )
aije t,
i ) I,...,M,R,P1,..., (2.5.39)
j)0
aij ) -Xij; j * 0
(2.5.40)
kTi )
jXij(i)
j)1
(2.5.41)
Nchem
kil ) -
jXlj
(i)
j)1
Nchem
kTi ) -
jaijbji
j)0
Nchem
kil )
(2.5.42)
jaljbji
j)0
Fernandez-Ramos et al.
cij(E)e t
xi(E,t) )
(2.5.47)
j)1
XR + X p + Xi ) 1
(2.5.44)
i)I
(2.5.45)
i)I
Thus one can calculate Xpj from eq 2.5.45; the other terms
in the equation come from the solution to the master equation,
as indicated above. These results, coupled with the longtime limits,
Xp() ) 1
XR() ) Xi() ) 0, (i ) I,...M)
dt
) E(0)kpi(E)xi(E,t)dE
i)I
(2.5.48)
dXp
dt
Nchem
e E
j t
j)1
(0)
i
i)I
kpi(E)cij(E)dE
(2.5.49)
Xp() )
Xpj
(2.5.50)
j)1
where
Xpj ) -
1 Nchem
(0)
i
kpi(E)cij(E)dE
(2.5.51)
(2.5.43)
(XR + Xp + Xi)j ) 0
dXp
j j)1
i)I
XR + Xp + Xi ) 0
(2.5.46)
Figure 14. Schematic diagram of the potential energy surface for C3H3 + C3H3 recombination.
Fernandez-Ramos et al.
Figure 15. The total rate coefficient for C3H3 + C3H3 f products.
N(E) ) (E - ER )
(3.1.4)
N(E) = R (E)
(3.1.5)
1
V ) ER - kR s2
2
(3.1.6)
(3.1.7)
k(E) ) [hR(E)]-1N(E)
k(T) )
0 exp(-E)FR(E)k(E)dE
R(T)
(3.1.1)
(3.1.2)
(3.1.8)
with
N(E) ) PRR(E)
(3.1.3)
R R
one can see clear structure in the rate constant that matches
well with the structure predicted by combining eqs 2.5.6,
3.1.5, and 3.1.7.395,566,567,909-912 These studies show clearly
that the quantized transition states control the structure of
the microcanonical rate constants as a function of energy.
Furthermore, they show that we can understand the stateto-state dynamics with the highest possible resolution allowed
by quantum mechanics, namely, from a specific channel of
reactants to a specific level of the quantized transition state,
to a specific channel of the product.566,567,912
Fernandez-Ramos et al.
PR(E) ) PRR(E)
(3.1.9)
k(T) ) PR(E)
(3.1.10)
k(T) )
PR(E)
k(T)
PR (E)
(3.1.11)
(3.1.12)
V VNR + E(el)
(3.2.1)
ip
(r,t) ) H(el)(r,R)(r,t)
(3.2.2)
12 ) (V1 - V2)/p|d12R4 |
U U
U ) U11 U12
12
22
(r,t) )
a(t)(r;R(t))
(3.2.3)
)1
|(r,t)| )
2
(3.2.4)
)1)1
d
) R4 R
dt
(3.2.6)
(3.2.7)
d ) |R|
(3.2.9)
(3.2.11)
specifically
1
V ) [(U11 + U22) - ((U22 + U11)2 2
4(U11U22 - U122))1/2] (3.2.12)
The transformation between adiabatic () and diabatic ()
wave functions is
(r;R) ) (r;R)T(R)
(3.2.5)
(3.2.10)
(3.2.13)
where
T(R) )
(3.2.15)
tan 2(R) )
2U12
U11 - U22
(3.2.15)
Fernandez-Ramos et al.
2U122
PLZ ) 1 - exp dU11 dU22
pZ
dZ
dZ
(3.2.16)
Fernandez-Ramos et al.
k2
A + B{\
}AB98Products
k
-D
(4.1.1)
k)
kDk2
k-D + k2
(4.1.2)
keq ) Kk2
(4.1.3)
d[B]
dR
J ) 4DABR2
(4.1.4)
kD ) 4DAB
(4.1.5)
Equation 4.1.5 is appropriate in the case where intermolecular forces are neglected for R > col. If V(col) cannot
be neglected, as for the reaction of two ions of charge qA
and qB for which
V(col) )
qAqB
col
(4.1.6)
k)
kDk2e-V(col)
kD + k2e-V(col)
(4.1.7)
k ) k2 exp[-V(col)]
(4.1.8)
(4.1.9a)
,o
) G,o
T (l) - GT (g) - RT ln [(T,l) - (T,g)]
(4.1.9b)
(4.1.10)
(4.1.11)
where the first delta in the last term, like that in eq 2.1.7,
denotes the difference between product and reactants, and
the second delta in this term, like the one in eq 4.1.10, refers
to the solvation process. By the quasithermodynamic analogue we also have
,o
o
G,o
T (l) ) GT (g) + GS
(4.1.12)
GoS(R,T)
(4.1.13)
(4.1.14)
(4.1.15)
for reactants, where Re is the equilibrium gas-phase geometry, and by the approximation
,o
o
G,o
T (l) ) GT + GS(R ,T)
(4.1.16)
for transition states, where R is the gas-phase transitionstate geometry. For the second term of eq 4.1.9b, the effective
potential used to calculate the transmission coefficient is
Fernandez-Ramos et al.
(4.1.17)
A(g) + S f AS
(4.2.1)
BS + AS f products
(4.2.2)
B(g) + AS f products
(4.2.3)
(4.2.4)
(4.2.5)
i)1
5. Concluding Remarks
There has been great progress in our ability to model the
kinetics of bimolecular reactions. This derives from (i)
improved methods for generating and using reactive potential
energy surfaces, especially implicit potential energy surfaces
generated by direct dynamics, (ii) improved dynamical
algorithms, including practical methods for finding variational transition states, well-validated multidimensional
methods for including tunneling, and master equation
methods for treating nonequilibrium distributions, especially
in multiwell, multi-arrangement reactions, and (iii) efficient
methods for interfacing i and ii. We anticipate continued
improvements in all three areas.
6. Glossary of Acronyms
Acronyms that are not used after they are defined are not
included here.
Glossary
B3LYP
C
C
CCUS
CRP
CSE
CUS
CVT
DFT
ESP
EVB
FR
G
GT
HF
HO
HR
IC
ICVT
IERE
ER
ILCT1D
ILCT2D
Fernandez-Ramos et al.
LCG3
LCG4
LCT
LEP
LEPS
LH
MCCM
MCMM
ME
MEP
MM
MP2
MT
OMT
VT
NES
OMT
PES
PST
PT2
QCT
R
RODS
RRKM
SCDM
SCT
SES
S N2
SPT
SRP
TSH
TST
UD
US
VB
VCI
VRC
VTST
WFT
WKB
7. Acknowledgments
The authors are grateful to Yan Zhao, Jingzhi Pu and
Ahren Jasper for helpful assistance. A.F.-R. also thanks the
Ministerio de Educacion Ciencia for a Ramon y Cajal
Research Contract and for the research project #BQU200301639. The work at Sandia and the University of Minnesota
is supported by the Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy
Sciences of the U. S. Department of Energy. Sandia is a
multi-program laboratory operated by Sandia Corporation,
a Lockheed Martin Company, for the United States Department of Energys National Nuclear Security Administration
under Contract No. DE-AC04-94-AL85000. The work at the
University of Minnesota is supported by Grant No. DOEDE-FG02-85ER13579. Additional support was provided by
the Air Force Office of Scientific Research by a Small
Business Technology grant to Scientific Applications and
Research Assoc., Inc.
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