,
D
0
= 45.89 kcal/mol and b 4:432=r
0
eq
[28]. For the typical
tensile stress value of 25 kcal mol
1
A
1
studied by Bolton
et al., f 1:24D
0
=r
0
eq
[28]. For the CC bond in model poly-
ethylene (pe), r
0
eq
1:529 A
, D
0
= 83 kcal/mol and
b 2:94=r
0
eq
[74,75,51,76]. At the representative tensile
stress value of 1 GPa [2], f 0:053D
0
=r
0
eq
. We have studied
Morse chains with b values in the range 13. All the calcu-
lations reported here are carried out for the tensile stress
value f = 0.02.
The potential (1a) is plotted versus r in Fig. 1 for various
f values and b = 1. For f 6 f
crit
b
2
, potential (1a) has two
12 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
stationary points, one at the potential minimum r = r
eq
and
one at the saddle point, r = r
b2f b
_
f
_ _
r
0
eq
2a
r
z
1
b
ln
b
b2f b
_
f
_ _
r
0
eq
: 2b
As f increases, r
decreases while r
eq
increases slightly. The
depth of the potential well decreases from the zero-force
value D
0
until f reaches the critical value f
crit
, at which
point the well disappears completely. For b = 1 and
f = 0.02, we have r
eq
= 1.010 and r
= 5.595.
Now consider a linear chain of N atoms. For this system
with N P2 degrees of freedom, the conversion from inter-
nal (bond) coordinates r to external (lab-xed) coordinates
x is given by (see Fig. 2)
x
k
k
j1
r
j
; k 1; . . . ; N: 3
We assume that the potential between atoms is pairwise
Morse (nearest neighbors only) and that the tensile force
acts only on the outermost atom, giving a potential func-
tion for the chain
V x; f V
M
x
1
V
M
x
2
x
1
V
M
x
N
x
N1
f x
N
Nr
0
eq
4a
N
i1
V
M
r
i
f r
i
r
0
eq
: 4b
The force is distributed through the chain so that the po-
tential in each bond coordinate r
k
has the same functional
dependence on bond length as the one-particle potential
(1a). Hence the equilibrium bond length between any adja-
cent pair of atoms at the global minimum in the N P2
chain is just the equilibrium bond length for the one-
dimensional case. A similar equivalence holds for the crit-
ical bond length. For example, the equilibrium and saddle
congurations corresponding to breaking bond 1 are
x
k;eq
kr
eq
; k 1; . . . ; N; 5a
x
k;saddle
r
z
k 1r
eq
; k 1; . . . ; N: 5b
For a single tethered atom, Fig. 1 shows the existence of a
well-dened conguration space transition state for bond
breaking located at the top of the eective potential energy
barrier. For a chain of atoms under stress, there is an anal-
ogous critical conguration associated with the dissocia-
tion of each bond. Detailed static analyses of polymer
chains subject to tensile force (both constant strain and
constant stress) have been given [45,77]. Although the static
analysis leads to a clear view of the nature of certain impor-
tant cuts through the multibody potential (for example,
one bond stretched with all other bonds having equal dis-
placements from equilibrium), it provides limited insight
into fracture dynamics.
Contours of the N = 2 potential energy surface (PES),
Eq. (4a), as a function of the single-particle coordinates
x
1
and x
2
are plotted in Fig. 3a. There is a global minimum
corresponding to the bound chain and two saddle points
associated with the two possible bond dissociation path-
ways. Along the minimum energy pathway for breaking
of bond 1, both x
1
and x
2
coordinates increase, while the
path for breaking of bond 2 is approximately a vertical
line, x
1
$ const. Bound motions at the respective transition
states are approximately perpendicular to the minimum
energy paths (see below).
The potential energy barrier to dissociation, i.e., the
activation energy E
a
E
f
, is dened to be
E
f
V r
z
; f V r
eq
; f : 6
For any particular value of the force f, all energies are mea-
sured from the f-dependent minimum energy V(x
eq
(f)). For
b = 1 and f = 0.02 we have E
a
= 0.8881.
2.2. Hamiltonian
In single particle coordinates, the N-atom chain Hamil-
tonian is simply
Hx; f
N
i1
1
2m
i
p
2
i
V x; f ; 7
2 4 6 8 10
x
0.5
1
1.5
2
V
Fig. 1. Potential V(r, f) for a tethered Morse particle under tensile stress,
Eq. (1a). The unit of length is r
0
eq
, the zero-force Morse oscillator
equilibrium bond distance, and the unit of energy D
0
, the unperturbed
Morse dissociation energy. Force parameter f: f = 0 (black), f = 0.02 (red),
f = 0.04 (green), f = 0.06 (blue), f = 0.08 (purple), f = 0.1 (light blue). (For
interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
1 2 3 4 f
x
1
x
2
Fig. 2. Denition of single-particle coordinates {x
i
} for a tethered chain
of N = 4 atoms under tensile stress.
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 13
where p
i
is the momentum of particle i. We shall take all
particles to have the same mass m
i
= m. Fixing the unit
of mass species a unit of time; with D
0
r
0
eq
m 1,
the period of the harmonic oscillation at the bottom of
the Morse potential well with b = 1 is s
HO
2p=
2
p
.
Although the overall magnitudes of dissociation rate con-
stants depend on the value of the particle mass m, the ratios
of rate constants computed from two dierent methods
(e.g., trajectory and RRK) do not (see Section 6.1).
In terms of bond coordinates, the N-atom chain Hamil-
tonian is
Hr; f
1
2
p
2
r
1
N
k2
p
2
r
k
N1
k1
p
r
k
p
r
k1
N
i1
V
M
r
i
f r
i
r
0
eq
: 8
In terms of single-particle coordinates the kinetic energy is
therefore separable while the potential energy is nonsepara-
ble, whereas in bond coordinates the potential energy sep-
arates while the kinetic energy has coupling terms p
r
k
p
r
k1
.
3. RRKM and RRK dissociation rate constants
3.1. RRKM theory
The RRKM expression for the E and f-dependent
molecular fragmentation rate constant associated with
breaking of bond j is [3943]
k
RRKM
j
E; f
N
z
j
E E
qE
; 9
where N
z
j
E E
f
is the classical sum of states (phase
space volume) at the transition state for breaking of bond
j, E
f
is the force-dependent dissociation energy, and q(E) is
the classical density of states for the reactant region of
phase space,
qE
dNE
dE
; 10
with NE the classical sum of states (phase space volume)
at total energy E.
For an N-mode system, q has dimensions (qp)
N
/
J = (Js)
N
/J = (Js)
N1
s. The classical transition state
sum of states N
z
is the phase space volume for an
(N 1)-degree-of-freedom system at the critical congura-
tion, and has dimensions (qp)
N1
= (Js)
N1
. The ratio of
the two, which is the classical unimolecular rate dissocia-
tion rate constant as dened in (9), then has units of inverse
time, (Js)
N1
/((J s)
N1
s) = s
1
, as it should. The unit of
time used in our calculations, s
0
, is discussed in Section 4.1.
The quantum density of states q
Q
is obtained in the semi-
classical limit by dividing q by the volume of a phase space
cell. For an N mode system, q
Q
= q/h
N
. Similarly, the
quantum transition state sum of states is N
z
Q
N
z
=h
N1
. We therefore have
k
RRKM
N
z
q
h
n1
N
z
Q
h
n
q
Q
11a
1
h
N
z
Q
q
Q
; 11b
so that the usual expression for k
RRKM
, Eq. (11b), explic-
itly contains Plancks constant h [3943]. The absence of
Plancks constant in the formula (9) expressed in terms of
purely classical quantities is nevertheless appropriate and
entirely correct.
Broadly speaking, in order for the RRKM rate constant
expression to be valid it is necessary that k
rxn
(k
IVR
, i.e.,
the rate of intramolecular energy transfer should be greater
2 4 6 8 10 12
x
1
2
4
6
8
10
12
x
2
2 4 6 8 10 12
X
2
4
6
8
10
12
Fig. 3. Contour plot of the N = 2-particle potential energy surface, Eq. (4a), with f = 0.02. Saddle points 1 (red) and 2 (green) are also shown. (a) Single-
particle coordinates: {x
1
, x
2
}; (b) Jacobi coordinates: {n, X}. (For interpretation of the references to colour in this gure legend, the reader is referred to the
web version of this article.)
14 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
than the reaction rate. Many studies have been carried out
on the validity of RRKM theory (9) and the connection
between deviations from statisticality and intramolecular
dynamics (for example, the existence of bottlenecks to
intramolecular energy ow) [66,7883]. Our focus here is
on the validity of expression (9) for the particular case of
atomic chains under tensile stress [2830].
We shall consider energies low enough so that the disso-
ciation of two or more bonds is not energetically possible.
If the overall statistical rate constant for chain fragmenta-
tion via single bond dissociation is
k
RRKM
N
j1
k
RRKM
j
12
where the total number of decay channels is equal to the
number of bonds in the chain, then N(t), the number of
bound molecules at time t, exhibits exponential decay,
Nt N0 e
k
RRKM
t
: 13
In general we dene the overall dissociation rate constant,
when it exists, by
k
1
Nt
_
Nt 14a
N
j1
k
j
14b
1
Nt
N
j1
_ n
j
t; 14c
where n
j
(t) is the number of molecules that have dissociated
via channel j at time t. In a regime where the system exhib-
its exponential decay, the rate constant for dissociation via
channel j is given in terms of the branching ratio b
j
as
k
j
n
j
t
N
m1
n
m
t
k b
j
k: 15
3.2. RRK theory: a harmonic approximation to RRKM
theory
RRK theory is the harmonic limit of RRKM theory
[52]. We approximate the potential function V(x) by a sec-
ond order expansion about the potential minimum and
saddle points. At these critical points, linear terms vanish,
and we have
V
crit
V x
crit
1
2
N
i1
N
j1
Dx
i
Dx
j
o
2
V
ox
i
ox
j
_ _
xx
crit
16
There are N real normal mode (angular) frequencies for the
reactant, fx
i
g
N
i1
, and N 1 real frequencies, fx
z
i
g
N1
i1
, for
the transition state, together with a single imaginary fre-
quency associated with unstable motion o the saddle.
For an r-dimensional harmonic oscillator, frequencies
fx
i
g
r
i1
, the phase space volume NE at energy E is
NE
2p
r
r!
E
r
r
i1
x
i
; 17
so that the harmonic (RRK) approximation to the RRKM
rate constant (9) for dissociation via transition state a is
k
RRK
f
E; a
1
2p
N
i1
x
f ;i
N1
i1
x
z
f ;i
a
E E
f ;a
E
_ _
N1
; 18
where E
f ;a
is the critical energy for dissociation of bond a
under external force f. It should be noted that in our pres-
ent model with all atoms identical, E
f ;a
E
f
is the same for
all transition states because b and r
0
eq
are the same for each
term in potential (4a).
3.3. Computation of RRKM rate constant
3.3.1. Reactant phase space volume
To compute k
RRKM
f
E we must determine the reactant
phase space volume NE, from which the reactant density
of states can be obtained via Eq. (10). NE is the volume
of the region of phase space consisting of all points with
energy less than or equal to E:
NE
_
dx
1
dp
1
dx
2
dp
2
dx
N
dp
N
HE Hx; p 19
where H is the Heaviside step function. This integral has no
analytical solution for our system (cf. [84]), necessitating
use of either a harmonic approximation to the potential
or numerical (Monte Carlo) integration. As the validity
of the harmonic approximation versus the role of anhar-
monicity in the reactant density of states is an important
question when assessing the validity of RRKM theory for
treating stressed polymer chains [28,29], for comparison
with the harmonic approximation we shall evaluate the
fully anharmonic reactant density of states and transition
state sum of states essentially exactly using a numerical
Monte Carlo approach.
To evaluate the phase space volume numerically, we
consider a region (hypercube) in phase space M
0
with
volume V
0
large enough to contain all reactant phase
points with energy E 6 E
MC
max
. To compute NE, the phase
space volume as a function of energy, we determine the vol-
umes V
a
of subsets M
a
& M
0
containing phase points with
E 6 E
a
6 E
MC
max
, a = 1, 2, . . . , a
max
. If n
r
phase points
fx
i
; p
i
g
N
i1
2 M
0
are chosen randomly, and n
a
of these points
lie within M
a
, then, for large enough n
r
, the volume V
a
is
V
a
n
a
n
r
V
0
: 20
From the set of pairs fE
a
; V
a
g
amax
a1
, we can t the phase
space volume NE to a polynomial in E,
NE E
N
c
0
c
1
E ; 21
that is, harmonic oscillator phase space volume plus anhar-
monic corrections. The associated reactant density of states
is then obtained by dierentiating the tted NE with re-
spect to E. Details of the sampling procedure are further
discussed in Appendix A.
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 15
For N = 2, the congurational projection of M
0
is the
union of the rectangular region and adjacent triangular
region shown in Fig. 4. It should be noted that the sam-
pling procedure used for N = 35, which employs a simpler
phase space hypercube, gives approximately the same den-
sity of states for N = 2 as that obtained using the more
elaborate shape shown in Fig. 4.
Harmonic and anharmonic reactant densities of states
are shown for N = 25 in Fig. 5.
As mentioned above, we consider energies low enough
such that multiple bond breakages (3-body dissociation
when N = 2) do not occur. For f = 0.02, b = 1, this means
that the maximum energy we consider is E
MC
max
1:5281
(with respect to the f-dependent minimum energy).
3.3.2. Transition state sum of states
For determination of the phase space sum of states for
the transition state associated with channel 1, it is conve-
nient to transform to Jacobi coordinates
X
1
2
x
1
x
2
r
1
1
2
r
2
22a
n x
2
x
1
22b
P p
1
p
2
22c
P
1
2
p
2
p
1
22d
using the generating function [85,60]
F
2
x
1
; x
2
; P; P Px
2
x
1
1
2
Px
1
x
2
: 23
The Hamiltonian in the transformed coordinates is then
HX; P; n; P
P
2
4
P
2
V n; X; f : 24
The PES in Jacobi coordinates (Fig. 3b) indicates that the
conguration space transition state 1 can approximately be
dened by X
z
1
2
x
1
x
2
1
2
r
z
r
z
r
eq
r
z
1
2
r
eq
(=6.10 for f = 0.02 and b = 1), which is just the harmonic
approximation nonreactive normal mode. In single particle
2 4 6 8 10 12
x
1
2
4
6
8
x
2
Fig. 4. Conguration space projection (light blue) of the phase space
region used for sampling of coordinates in the Monte Carlo determination
of reactant phase space volume NE. Contours of the potential energy
and the location of saddles (saddle 1 (red) and saddle 2 (blue)) are also
shown. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)
0.25 0.5 0.75 1 1.25 1.5
E
20
40
60
80
100
120
140
N 2
0.25 0.5 0.75 1 1.25 1.5
E
100
200
300
400
500
N 3
0.25 0.5 0.75 1 1.25 1.5
E
200
400
600
800
1000
N 4
0.25 0.5 0.75 1 1.25 1.5
E
250
500
750
1000
1250
1500
N 5
Fig. 5. Harmonic approximation (red) and fully anharmonic Monte Carlo (blue) reactant density of states versus energy for (a) N = 2, (b) N = 3, (c)
N = 4 and (d) N = 5. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
16 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
coordinates, the conguration space projection of transi-
tion state 1 lies along the line x
2
= x
1
+ 2r
+ r
eq
.
The 2D hypercube M
z
0
used to sample transition state
1 is dened by conditions
X r
z
1
2
r
eq
25a
n 2 0; r
z
25b
P 0 25c
P 2
E
MC
max
E
f
_
;
E
MC
max
E
f
_ _ _
25d
Thus the N = 2 transition state 1 hypercube has volume
V
z
0;1
2r
z
E
MC
max
E
_
. The transition state 2 sampling
hypercube is dened as
x
1
2 0; 3:303 26a
x
2
r
eq
r
z
26b
p
1
2
2 E
MC
max
E
f
_ _
_
;
2 E
MC
max
E
f
_ _
_ _ _
26c
p
2
0; 26d
and has volume V
z
0;2
6:606
2E
max
E
_
. Again, the x
1
range endpoint of 3.303 marks the position of the barrier to
3-body dissociation products from transition state 2 for
f = 0.02 and b = 1.
For both the reactant and transition state Monte Carlo
calculations, we used a
max
= 100, with n
rand
= 10
7
. Transi-
tion state sums of states are tted to functions of the form
NE E
z
f
E E
z
f
N1
c
0
c
1
E E
z
f
: 27
4. Classical trajectory simulations
4.1. Integration of trajectories
Classical equations of motion are
_ z L
H
z fz; Hzg: 28
with z = (x
1
, . . . , x
N
,p
1
. . . p
N
) and Hamiltonian H(z) given
by Eq. (7). Here, {,} denotes the usual Poisson bracket
[85,60]. We employ a simple reversible 2nd-order symplec-
tic integrator [86,87] to integrate Eq. (28). A typical value
of the timestep used in our integrations is h = 0.1s
0
, where
s
0
is the unit of time associated with our choice of units for
energy, length and mass. In units of s
0
, the period of mo-
tion of a unit mass in the harmonic potential obtained by
expanding the Morse potential about its minimum is
s
HO
2p=b
2
p
. For example, using physical parameters
for model polyethylene [74,75,51,76] we have s
HO
1.5s
0
46.4 fs. With h = 0.01 s
0
and n
step
= 8 10
3
time-
steps, the length of our typical trajectory runs is then
approximately 55 harmonic oscillator periods 2.5 ps.
For the tensile stress values used here, this timescale is long
enough to characterize the decay dynamics.
4.2. Sampling phase points on the energy shell
To compare the predictions of RRK and RRKM theory
at constant energy E with trajectory results, it is necessary
to sample trajectory initial conditions z = (x, p) distributed
with suitable measure on the energy shell H(z) = E. The
sampling procedure used is discussed in more detail in
Appendix B.
4.3. Extraction of rate coecient k(E)
Given a microcanonical ensemble of N(0) initial condi-
tions fz
j
0g
N0
j1
, and dening N(t) 6 N(0) as the number
of trajectories that have not reacted by time t, we can com-
pute an eective rate constant k(E, f) if we assume that the
system exhibits exponential decay with time-independent
rate constant. The associated lifetime distribution is
Nt N0 expkE; f t: 29
For each energy we run N(0) = 50,000 trajectories and re-
cord the times at which dissociation of each trajectory oc-
curs (if it ever does for that trajectory). For f = 0.02 and
b = 1 the condition for dissociation of bond j is taken to be
r
j
> r
z
2r
0
eq
; j 2 1; . . . ; N: 30
The resulting data are histogrammed. Transient behavior
(the rst 350 time steps for b = 1 and f = 0.02) is ignored
and an exponential t to the histogram at longer times
gives approximate k(E, f) values.
It should be noted that the bond dissociation criterion
(30) is intended to ensure that recrossing eects are
excluded from the numerical determination of the long-time
(asymptotic) decay rate, which is the quantity to be com-
pared with statistical theories.
Values of the decay rate constants obtained via trajec-
tory simulation are compared with the predictions of statis-
tical theory below. We also compare these dynamical decay
rates with those obtained via an analysis based on the clas-
sical spectral theorem [6673].
5. Phase space structure and dynamics for N = 2
Before turning to a detailed comparison of RRKM and
trajectory dissociation rate constants, we examine the
phase space structure for the N = 2 chain. For the tethered
chain with N = 2 atoms, we can use the standard Poincare
surface of section (SOS) construction [60] to examine the
system phase space at constant energy E.
5.1. Surfaces of section
5.1.1. SOS along a dissociative coordinate: PODS and
turnstiles
At constant energy E, we can dene a SOS by the con-
dition (given in terms of Jacobi coordinates)
P 0;
_
P > 0: 31
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 17
We will refer to this SOS as SOS
1
. Fig. 6 shows SOS
1
for
f = 0.02, b = 1 at energies E E
f
0:4, E
f
, E
f
0:01
and E
f
0:1.
The overall shape of the separatrix [60] dening the reac-
tant phase space region [79] is clearly visible in Fig. 6b,
E E
f
. The critical conguration for dissociation via tran-
sition state 1 is located on SOS
1
at P = 0, X = 6.10. At
energies above the activation barrier, the periodic orbit
dividing surface (PODS [8890]; see below) appears as an
unstable xed point on SOS
1
(Fig. 6c and d); the PODS
and its associated stable/unstable manifolds are computed
below. The points spilling out towards X !1 are reactive
trajectories that dissociate via breaking of bond 1.
For E > E
f
we also see lobe or turnstile structures
near the boundaries of the reactive complex region. The
turnstiles mediate transport between phase space regions,
and detailed analysis of turnstile dynamics can be used to
understand rates of intramolecular energy ow and unimo-
lecular dissociation [91,79,92]. Regions of lower trajectory
density in SOS
1
are associated with trajectories that disso-
ciate through channel 2, and so do not return to the SOS
(see below).
Also evident in the interior of the complex region is an
area of bounded, regular behavior, which appears as a
transverse slice through a set of invariant tori [60]. Classical
trajectories with initial conditions on invariant tori do not
Fig. 6. Surfaces of section for the N = 2 chain (f = 0.02). Conjugate variables (X, P) are plotted when SOS
1
conditions P = 0,
_
P > 0 are satised. (a)
E E
f
0:4; (b) E E
f
; (c) E E
f
0:01; (d) E E
f
0:1.
18 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
dissociate. The fact that a signicant proportion of the
tethered chain phase space volume is occupied by bound
trajectories means that, to obtain a more accurate predic-
tion of the dissociation rate constant using statistical
assumptions, it is necessary to correct RRKM theory by
removing bound phase space regions from consideration
[9395,79,96].
SOS
1
is symmetric about the line P = 0; this time-rever-
sal symmetry can be exploited to determine relevant peri-
odic orbits [97,98]. (An analogous SOS suitable for
channel 2, SOS
2
, is dened by the conditions p
1
= 0,
_ p
1
> 0. Whereas SOS
1
is symmetric about the line P = 0,
SOS
2
is symmetric about the line p
2
= 0.)
In the (X, P) plane of SOS
1
, the unstable xed point on
the line P = 0 is the intersection of the PODS [8890] asso-
ciated with the transition state for bond 1 cleavage with the
SOS. This hyperbolic xed point and its associated stable/
unstable manifolds (plus the analogous structures for reac-
tion 2) are phase space structures that determine the disso-
ciation dynamics of the N = 2 tethered chain.
Consider determination of the PODS for channel 1. To
locate the PODS, we sample a line of initial conditions on
SOS
1
along the symmetry line P = 0. The SOS conditions
on P and P imply that points on the symmetry line have
p
1
= p
2
= 0, so that these trajectories start on the classical
zero-velocity manifold V(x) = E. Any trajectory that
returns to the symmetry line in a single iteration of the
Poincare map is a periodic orbit [97,98]. The location of
the PODS on the symmetry line can therefore be deter-
mined using a NewtonRaphson procedure [99].
Fig. 7 shows conguration space projections of PODS
associated with both transition states at several energies.
The shapes of the PODS conform approximately to the har-
monic prediction of a slanted line segment for transition
state 1 and an approximately horizontal line segment for
transition state 2. Close inspection of the PODS reveals that
they are in fact curved, an anharmonic dynamical eect.
Numerical approximations to the stable/unstable mani-
folds W
u=s
of the PODS are obtained by propagating phase
points close to the periodic orbit on the respective linear-
ized manifolds (computed as outlined in Appendix C) for-
wards/backwards in time [60]. To visualize W
u=s
, we select
1000 initial conditions along short segments of the linear-
ized manifolds E
u/s
close to the PODS and propagate all
these phase points either forward or backwards in time.
The resulting manifolds for E
f
0:1 are shown in Fig. 8.
Taken together, these two manifolds dene a bound com-
plex region. One possible denition of a direct trajectory
is one that does not enter or exit the bound separatrix
region via a turnstile [79].
5.1.2. SOS in reactant region (r
1
= r
2
): reactive cylinders
An informative view of the dynamics is provided by the
SOS dened by crossings of the hypersurface
R
+
{z|r
1
= r
2
, _ r
2
> _ r
1
g. To formulate the crossing condi-
tion in terms of a single variable, we consider a canonical
transformation to coordinates
X
1
2
x
1
x
2
32a
Dr r
2
r
1
x
2
2x
1
32b
with generating function [60,85]
F
1
2
x
1
x
2
P x
2
2x
1
p
Dr
; 33
from which we deduce the relation between conjugate
momenta
P
2
3
p
1
2p
2
34a
p
Dr
1
3
p
2
p
1
: 34b
1 2 3 4 5 6 7 8
x
1
6.4
6.6
6.8
7.2
7.4
7.6
7.8
x
2
Fig. 7. PODS shown together with potential energy contours for f = 0.02.
Saddle points 1 and 2 are marked as black dots, PODS
1
and PODS
2
are
shown at energies E E
f
0:1 (red), E
f
0:2 (green), E
f
0:3 (blue),
E
f
0:4 (yellow), E
f
0:5 (purple) and E
max
(black). (For interpretation
of the references to colour in this gure legend, the reader is referred to the
web version of this article.)
Fig. 8. SOS (green) at E E
f
0:1 dened by P = 0,
_
P > 0; The stable
manifold W
s
(blue) and unstable manifold W
u
(red) of the PODS are also
shown. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 19
(Note that the momentum P conjugate to X in the {X, Dr}
coordinate system diers from the momentum P in the
{X, n} coordinate system.) From the nondiagonal kinetic
energy
T
P
2
4
Pp
Dr
2
5p
2
Dr
2
; 35
we have
p
Dr
1
10
P
1
10
40T 9P
2
_
: 36
We select the positive branch of solutions for p
Dr
, which is
equivalent to imposing the surface crossing condition
p
Dr
>
1
10
P or
p
2
> 2p
1
; 37
which is just the condition p
2
p
1
> p
1
i.e. _ r
2
> _ r
1
. Thus,
an equivalent denition of our surface is R
+
{z|Dr = 0,
p
Dr
1
10
P
1
10
40T 9P
2
p
g. We examine the fate of trajec-
tories initiated on a grid of initial conditions with
r
1
0 r
2
0 x
1
0
1
2
x
2
0 2 0; 3:5 38a
P0 2 2:6; 2:6; 38b
where r(0) and P(0) values are evenly-spaced. Initial mo-
menta {p
1
(0),p
2
(0)} are obtained from
p
1
P
2
2p
Dr
39a
p
2
P
2
p
Dr
; 39b
where the p
Dr
(0) values are chosen to be on the positive
branch of (36) so as to place the initial conditions on R
+
.
The resulting initial grid is shown in Fig. 9a, and the
SOS generated from this initial condition set is in Fig. 9b.
A plot of the grid of initial conditions on R
+
under one
iteration of the return map is shown in Fig. 9c. One note-
worthy feature of Fig. 9b is the presence of holes, regions
within the SOS structure that are either devoid of or spar-
sely lled by iterates.
To elucidate the dynamical signicance of these holes,
we initiate trajectories on transition states 1 and 2 (that
is, distributed along the corresponding PODS), propagate
them forward in time, and examine their intersection with
R
+
. The successive intersections of these trajectories with
the SOS are shown in Fig. 10. Let R
u;j
m
& R
be the region
corresponding to the mth intersection of R
+
by the set of
trajectories initiated on transition state j. (The superscript
u indicates that the region R
u;j
m
is bounded by the intersec-
tion of the unstable mainfold of the PODS with R
+
.)
Fig. 10a shows that R
u;1
1
and R
u;2
1
are the two holes toward
the bottom of the SOS structure that contain no phase
points; that is, regions R
u;1
1
and R
u;2
1
are composed of phase
points with no pre-image on R
+
. The regions R
u;1
2
and R
u;2
2
,
rst visible in Fig. 10b, are cross sections of cylindrical
structures in phase space, so-called reactive cylinders [61
65]. Upon further iterations, shown in Fig. 10ce, the cyl-
inder cross sections stretch out, twist and generally spread
themselves through the reactive region. We infer that the
set of reactive phase points on R
+
is the closure of
2
j1
1
i1
R
u;j
i
.
Of equal importance to the sets R
u;j
m
, j = 1, 2, which react
through transition states 1 and 2, respectively, in negative
time, is the set of trajectories R
s;j
m
, which react in forward
time. We dene R
s;j
m
to be the set of trajectories that react
through transition state j after undergoing m 1 further
intersections with R
+
. (The superscript s indicates that
these trajectories are associated with the stable manifold
of the corresponding PODS; they are calculated by propa-
gating backwards in time from the relevant transition
state.) In particular, we consider the regions R
s;j
1
, j = 1, 2,
which consist of phase points that react immediately in for-
ward time, where immediate means without an intervening
intersection of the SOS.
Fig. 11a displays R
s;1
1
R
s;2
1
along with the grid of initial
conditions on R
+
that intersect R
+
for some positive time
value. Note that R
s;1
1
R
s;2
1
lls the holes in the SOS,
which consist of phase points that never return to the sur-
face in positive time, and so react immediately.
It is informative to observe intersections between the
forward and backward direct reactive tubes, R
u;1
2
R
s;1
1
and R
u;2
2
R
s;2
1
. (One could just as well inspect the intersec-
tions R
u;1
1
R
s;1
2
and R
u;2
1
R
s;2
2
, which appear in ure
Fig. 11b and are simply the time-evolved iterations of
R
u;1
2
R
s;1
1
and R
u;2
2
R
s;2
1
, respectively for one mapping of
R
+
.) To illustrate the information aorded by these over-
laps, the area AR
u;1
2
R
s;1
1
reects the phase space volume
of trajectories that enter the reactant region through tran-
sition state 1 and exit through transition state 1 after
2 + 1 1 = 2 intersections with the SOS R
+
. Hence,
AR
u;1
2
R
s;1
1
AR
u;2
2
R
s;1
1
should correlate with the
fraction P
z
1;d
E E
f
of transition state 1 belonging to
direct trajectories, where direct trajectories could be
dened as those having only two intersections with SOS
R
+
, noting that since R
i;u
1
R
s;j
1
for i, j = 1, 2 is zero, no
reactive trajectories cross R
+
only once.
We observe from Fig. 12 that the overlap areas
R
u;1
2
R
s;1
1
and R
u;2
2
R
s;2
1
both increase with increasing
energy, while R
u;2
2
R
s;1
1
and R
u;1
2
R
s;2
1
are zero for most
energies except those near E
max
, where a thin strip of non-
zero overlap R
u;2
2
R
s;1
1
begins to emerge, as is evident in
Fig. 12df. Thus, there are virtually no trajectories that
enter through transition state m and exit through transition
state n, m5n, without crossing SOS R
+
at least three times.
6. Statistical theories compared with dynamical rate
constants
6.1. Ratios of rate constants are independent of choice of
mass unit
We shall compare absolute values of dissociation rate
constants obtained from classical trajectory simulations
with those calculated using RRKM-type theories. Recall
that our unit of time is dened in terms of the choice of
20 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
mass unit, s
0
$
m
p
. Although absolute values of dissocia-
tion rate constants depend upon the value of m used, ratios
of rates do not. Thus, from Eq. (18) for the RRK rate con-
stant, and recalling the mass dependence of harmonic oscil-
lator frequencies, we see that
k
RRK
f
E $
1
m
p
_ _
N
1
m
p
_ _
N1
$
1
m
p : 40
The RRKM rate constant is given by the ratio (9). Both the
reactant phase space volume and the density of states q(E)
scale in general as
m
p
N
, where N is the number of degrees
of freedom, while N
z
E E
f
scales as
m
p
N1
. The
anharmonic RRKM rate constant therefore scales in the
same way with mass as the RRK rate constant, as 1=
m
p
.
Finally, to determine the mass dependence of simulation
results k
sim
, we note that increasing m means that particles
are eectively moving more slowly by a factor of 1=
m
p
; we
therefore have k
sim
$ 1=
m
p
.
Rate constants k
RRK
, k
RRKM
, and k
sim
therefore all
have the same mass dependence and the ratio of any two
of these k values is mass-independent.
6.2. Comparison of RRK with RRKM and simulation rate
constants
RRK, RRKM and simulation rate constants for the
total dissociation rate for N = 2, f = 0.02, b = 1 are shown
Fig. 9. (a) Grid of initial conditions for E E
f
0:1 on SOS dened by r
1
= r
2
, _ r
2
> _ r
1
. (b) SOS for E E
f
0:1 dened by r
1
= r
2
, _ r
2
> _ r
1
. (c) First
iterate under Poincare map of initial conditions in panel (a).
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 21
Fig. 10. The nth crossing of SOS r
1
= r
2
, _ r
2
> _ r
1
for trajectories initiated on transition states 1 (red) and 2 (blue), E E
f
0:1. (a) n = 1; (b) n = 2; (c)
n = 3; (d) n = 4; (e) n = 10. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
22 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
as functions of energy in Fig. 13a. While the harmonic
RRK approximation signicantly overestimates the
RRKM rate constant (cf. Refs. [2729]), the RRKM value
is only slightly larger than the simulation results, with the
disparity growing larger at higher energies. This level of
agreement is perhaps surprising, given the non-negligible
fraction of regular phase space occupied by invariant tori,
as noted above. We comment further on this point below.
6.3. Relative rate calculations
As the phenomenon of reactive selectivity is of central
interest in chemistry, it is important to examine the relative
rates of competing reactions. For N = 2, the two compet-
ing reactions are the cleavage of bonds 1 and 2, respec-
tively. We therefore study the ratio of rate constants k
2
/
k
1
. We consider the statistical predictions for the branching
ratio k
2
/k
1
and compare with simulation results.
6.3.1. RRK and RRKM calculations, N = 2
From expression (9) for k
RRKM
(E, f), the ratio of
RRKM rate constants for reactions 1 and 2 is simply
k
2
k
1
_ _
RRKM
N
z
2
E E
N
z
1
E E
; 41
as the reactant density of states at energy E cancels out.
The ratio in the harmonic approximation is then
k
2
k
1
_ _
RRK
x
z
1
x
z
2
; 42
where x
z
j
is the harmonic frequency of the nonreactive nor-
mal mode taken about the jth saddle point.
6.3.2. Trajectory results
If k
sim
is the total rate constant for dissociation as deter-
mined from trajectory simulation, the rate constants for
channels 1 and 2, k
1,sim
and k
2,sim
respectively, are given
in terms of the respective branching ratios multiplied by
the overall rate constant:
k
j;sim
n
j
n
1
n
2
k
sim
; j 1; 2 43
where n
1
, n
2
are the number of trajectories that have re-
acted through channels 1, 2 respectively at some relatively
long time (we use 2000 time steps) with all nonstatistical,
transient trajectories omitted. The rate ratio is then
k
2
k
1
_ _
sim
n
2
n
1
: 44
6.3.3. Periodic orbit dividing surface actions
If the transition state of (locally) minimal ux at energy
E is the phase space region A, then for the N = 2 case it
follows from the variational principle of classical mechan-
ics [100] that the boundary oAof the region Ais a periodic
classical trajectory dening the periodic orbit dividing sur-
face (PODS) [88,89]. The associated ux is then the action
of the PODS
N
z
PODS
E E
f
_
A
dp ^ dq
_
oA
pdq 45
dened as a line integral over one cycle of the PODS. Be-
cause the PODS is a dynamically determined object and
N
z
PODS
E E
f
reects the full anharmonic dynamics in
the vicinity of the saddle point, this method for calculating
the sum of states N
z
E E
f
provides a check on the accu-
Fig. 11. (a) Grid of initial conditions of trajectories started on the SOS r
1
= r
2
, _ r
2
> _ r
1
, E E
f
0:1, and returning to the SOS at least once, is shown in
green. Trajectories in red and blue regions dissociate immediately through transition states 1 (red) and 2 (blue), respectively, in forward time. (b) Iterates of
initial conditions in panel (a) are shown in green. Additional red and blue regions are preimages of regions in panel (a) under Poincare map; that is, they
contain initial conditions for trajectories that dissociate after crossing the SOS once in forward time. (For interpretation of the references to colour in this
gure legend, the reader is referred to the web version of this article.)
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 23
Fig. 12. Red points are initial conditions for trajectories having at least one intersection with the SOS r
1
= r
2
, _ r
2
> _ r
1
. Green points are the iterates under
the Poincare map. E E
f
DE. (a) DE = 0.1; (b) DE = 0.2; (c) DE = 0.3; (d) DE = 0.4; (e) DE = 0.5; (f) DE = 0.6. (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this article.)
24 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
racy of the corresponding harmonic and Monte Carlo cal-
culations. We evaluate the PODS sum of states at energy E
as
_
PODS
p
1
_ q
1
dt p
2
_ q
2
dt
_
PODS
p
2
1
p
2
2
j
HE
dt; 46
using PODS initial conditions obtained as described above.
Fig. 14 shows N
z
j
E E
f
, j = 1, 2, versus energy E for
the harmonic approximation, Monte Carlo integration and
the PODS action method just described. We see that the
anharmonic Monte Carlo areas agree essentially exactly
with the PODS actions (the true dynamical local uxes).
It is also evident that the harmonic approximation to the
transition sum of states is reasonably accurate, especially
at lower energies.
Fig. 15 shows the RRK and PODS branching ratios k
2
/
k
1
versus energy compared with simulation results. The
value of the RRK branching ratio
2
p
is essentially deter-
mined by the ratio of the reduced masses for breaking
bonds 1 and 2, and is independent of energy (cf. Ref.
[28]). To the extent that motion along the PODS (the
dynamically dened conguration space transition states)
corresponds to separable motion along the bond coordi-
nates, the RRKM/PODS branching ratios will be identical
with the harmonic value. This is not quite the case, how-
ever, as can be seen from the form of the PODS plotted
in Fig. 7, so that the branching ratios calculated from the
PODS are close to but not identical with the RRK value.
Only the ratio obtained from simulations exhibits any
signicant energy dependence; further analysis of its
dynamical origins will require a more detailed investigation
of lobe dynamics [92] via the surface of section shown in
Fig. 9.
7. Correcting RRKM theory
7.1. General considerations
While Fig. 6ad show that a nonnegligible portion of the
reactant phase space is occupied by regular, bound trajec-
tories, RRKM rate constants for bond dissociation calcu-
lated using an anharmonic density of states are in fairly
close agreement with trajectory values, at least for N = 2
(see Fig. 13ad). Given that the reactant phase space is cer-
tainly not globally chaotic, and given the probable exis-
tence of barriers to IVR in the vicinity of the regular
regions of phase space (cantori [91,79]), it is possible that
the good agreement between RRKM and trajectory rate
constants is to some degree fortuitous.
In order to explore this point further, and to make a
proper comparison between the statistical rate constant
and the dynamical result, we need to ensure that the inu-
ence of bound and direct trajectories on the RRKM-type
calculation is taken into account. A noteworthy discussion
of this problem has been given by Berblinger and Schlier in
the context of the dissociation of the H
3
molecule [96].
0.1 0.2 0.3 0.4 0.5 0.6
E E
f
0.025
0.05
0.075
0.1
0.125
0.15
k
N 2
0.1 0.2 0.3 0.4 0.5 0.6
E E
f
0.02
0.04
0.06
0.08
k
N 3
0.1 0.2 0.3 0.4 0.5 0.6
E E
f
0.005
0.01
0.015
0.02
0.025
k
N 4
0.1 0.2 0.3 0.4 0.5 0.6
E E
f
0.005
0.01
0.015
0.02
k
N 5
a b
c d
Fig. 13. k
RRK
E E
f
(red), k
RRKM
E E
f
(blue) and k
sim
E E
f
(green) for (a) N = 2, (b) N = 3, (c) N = 4 and (d) N = 5. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of this article.)
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 25
Barblinger and Schlier identify various properties of the
reactant phase space that should be taken into account
when computing a statistical, RRKM-type dissociation
rate constant. These factors are: (a) presence of direct reac-
tive trajectories; (b) recrossing of the transition state(s); (c)
existence of bound (nonreactive) regions of reactive phase
space. After corrections for all these factors have been
made, any remaining discrepancies between RRKM theory
and simulation results can be presumably be attributed to
dynamical eects such as slow IVR (existence of signicant
phase space bottlenecks) in the reactive portion of phase
space.
The analysis of Berblinger and Schlier can be summa-
rized in the following formula for the corrected RRKM
dissociation rate constant [96,80]
k
RRKM
corrected
k
RRKM
j
1 /
z
direct
1 /
bound
/
direct
; 47
where /
bound
is the fraction of the reactant phase space re-
gion occupied by bound (unreactive) trajectories, /
direct
is
the fraction of phase space occupied by direct (nonstatis-
tical) trajectories, /
z
direct
is the fraction of the phase space
at the transition state occupied by direct trajectories, and j
is a factor that corrects for recrossing of reactive trajecto-
ries at the transition state (the transmission coecient).
Rather than attempt to implement a corrected statistical
rate theory in the form given by Berblinger and Schlier, we
now discuss a related approach for the N = 2 chain based
on the classical spectral theorem [6673].
7.2. Computation of statistical and dynamical rate constants
via the classical spectral theorem
In classical unimolecular rate theory it has been known
at least since the work of Thiele [66] that the appropriate
invariant measure on the energy shell for reactive trajecto-
ries is given by the volume element (see also refs [6773])
dr dq
z
^ dp
z
^ dt; 48
where (q
,p
f
hti
1
N
z
2
E E
f
hti
2
; 49
where N
z
i
E E
f
is the sum of states for transition state i
and hti
i
is the average gap time for trajectories that leave
the reactant region via transition state i (in forward time)
0.1 0.2 0.3 0.4 0.5 0.6
E E
f
0.5
1
1.5
2
2.5
1
f
(red),
N
z
1;anh
E E
f
(blue) and N
z
1;PODS
E E
f
(black circles) versus E; (b)
Sum of states for transition state 2. N
z
2;HO
E E
f
(red), N
z
2;anh
E E
(blue) and N
z
2;PODS
E E
f
(black circles) versus E. (For interpretation of
the references to colour in this gure legend, the reader is referred to the
web version of this article.)
0.1 0.2 0.3 0.4 0.5 0.6
EE
f
*
0.8
1.2
1.4
1.6
1.8
k
2
k
1
Fig. 15. Branching ratio k
2
/k
1
as a function of energy above threshold,
E E
f
, f = 0.02. HO approximation (red); anharmonic Monte Carlo
(blue); PODS actions (black circles); trajectory simulation (green circles).
(For interpretation of the references to colour in this gure legend, the
reader is referred to the web version of this article.)
26 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
having entered through either channel. Eq. (49) may be
interpreted as an expression for the combined volume of
two (bifurcated) reactive cylinders [6163] with cross-sec-
tional areas N
z
i
E E
f
and lengths hti
i
, i = 1, 2.
The density of states dened in Eq. (49) excludes bound
regions of phase space, as bound trajectories by denition
do not pass through the transition state; direct trajectories,
however dened, are still included.
By initiating trajectories on transition state j, we can
determine N
(j)
(t), the number (or fraction) of unbound spe-
cies left at time t that will ultimately decay through channel
j. It is straightforward to show that, whereas products in
channel j appear at rate characterized by the constant k
j
,
the subpopulation of reactive species that dissociate
through channel j undergoes the same exponential deple-
tion exp(k t) as the overall reactant concentration.
For those reactant species destined to dissociate through
channel j, a suitably normalized distribution of gap times is
(assuming an exponential distribution [66])
f
j
t; E
expkEt
_
1
tc
expkEt
0
dt
0
; 50
where t
c
> 0 is a cuto time beyond which all transient,
nonexponential behavior has died out. The average gap
time for reaction through channel j is then given by
hti
j
E; t
c
_
1
tc
t
0
f
j
t
0
; Edt
0
1
kE
t
c
; 51
and depends on the cuto time t
c
. The values of k(E) ob-
tained with this method are denoted by k
PODSj
1
E, where
the notation indicates that the intercept 1/k is in practice
obtained by tting the observed linear behavior of hti
j
at
large cuto times t
c
!1 and extrapolating back to nd
the intercept. A representative plot of hti
j
(E) versus t
c
(Fig. 16) shows transient, nonexponential behavior for
shorter t
c
values and linear behavior corresponding to
exponential decay for larger t
c
values.
Also of interest is the quantity k
0
(E), the statistical dis-
sociation rate constant corrected for the presence of bound
regions of reactant phase space (and obtained via the spec-
tral theorem with t
c
= 0). By denition of the average gap
time, q
(j)
(E), the portion of the reactant density of states
destined for dissociation through channel j, is given by
q
j
E N
z
j
E E
f
hti
j
E; 52
where hti
j
(E) is obtained with t
c
= 0, so that all direct
trajectories are included in the average. The rate constant
k
0
(E) is obtained from
k
0
E
N
j1
N
z
j
E E
N
j1
q
j
E
: 53
7.3. Comparison of statistical and dynamical dissociation
rates for N = 2
Total dissociation rate constants for N = 2, f = 0.02 and
b = 1 obtained using various methods are shown in Fig. 17.
We can see that there is a signicant (roughly threefold)
disparity between the RRK and the RRKM predictions,
representing a qualitative failure of the harmonic approxi-
mation. This is not unexpected, as the harmonic approxi-
mation is especially inadequate for the reactant region
(see Fig. 5ad). At xed energy per mode, e = E/N, the dis-
parity between harmonic and anharmonic statistical rate
theory increases with the number of atoms N (see below).
If we consider the reactant density of states for N = 2, it
should apparently always be the case that
q
1
E q
2
E 6 qE; 54
as the RHS of (54) includes bound as well as non-bound
phase points, so that we expect the inequality
k
0
E Pk
RRKM
E 55
to hold. As we can see in Fig. 17, inequality (55) holds only
up to a certain energy, E E
f
0:4, above which the rate
20 40 60 80 100
t
c
50
100
150
200
250
300
t
1
Fig. 16. Plot of average gap time hti
1
(t
c
) as a function of cuto time t
c
for
trajectories initiated on PODS
1
, E E
f
0:4. Note linear behavior
consistent with exponential decay as t
c
!1.
0.1 0.2 0.3 0.4 0.5 0.6
EE
f
*
0.025
0.05
0.075
0.1
0.125
0.15
k
Fig. 17. Rate constants k
RRK
E E
f
(red), k
RRKM
E E
f
(blue),
k
sim
E E
f
(green circles), k
0
E E
f
(black circles) and k
PODS1
1
E E
F
, for N = 2, f = 0.02 and
b = 1. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 27
constant k
0
(E) actually becomes smaller than the RRKM
rate constant. We resolve this apparent paradox by noting
that q(E) is calculated using the xed conguration space
sampling region shown in Fig. 4, while the densities q
(j)
are obtained via the spectral theorem using the PODS.
As the PODS move progressively outwards from their
respective saddle points with increasing energy, the increase
of the associated densities of states with energy is sucient
to outweigh the eects of the presence of bound regions,
resulting in a violation of the inequality (55).
The anharmonic RRKM results are close to total disso-
ciation rate constants determined via simulation. However,
the RRKM results begin to disagree with the simulation
rates with increasing energy, the disparity eventually reach-
ing a factor of roughly three. This is perhaps not surpris-
ing, given the lack of global chaos seen in the SOS for
N = 2. At the very highest energies, it becomes dicult to
t the lifetime distributions to a pure exponential decay;
nevertheless, the ts obtained for k
sim
and k
0
agree at these
energies.
Dissociation rate constants obtained using the classical
spectral theorem essentially match those obtained by simu-
lation. Of course the spectral theorem approach, which is
based upon the distribution of gap times, must reect the
same dynamical information as a standard trajectory sim-
ulation. It is nevertheless gratifying to see that the two
approaches agree so well. It seems likely that the spectral
theorem approach will prove useful in the multimode case
(N P3 dof) in combination with the normal form based
analysis of the transition state of Uzer et al.[102,103].
8. N >3 atom chains
A signicant jump in dynamical complexity occurs in
going from N = 2 to N P3-atom chains. For N > 2, the
dynamics and phase space structure cannot easily be visu-
alized via a SOS [60,104]. Further, the transition states
for chain fragmentation are themselves (N 1) P2-degree
of freedom dynamical systems, making visualization and
accurate anharmonic sampling dicult using the
approaches described above for N = 2 atom chains.
Accurate determination of transition states in N-atom
chains under tensile stress is a problem that seems well-sui-
ted to the application of recent advances in normal form
expansion techniques recently developed by Uzer
et al.[102,103,105]. In the present work, however, we
restrict ourselves to the computation of a hybrid har-
monicanharmonic rate constant for our statistical predic-
tions of chain fragmentation rates.
As Fig. 14 shows, for N = 2 at least the harmonic tran-
sition state sum of states is a close approximation to the
anharmonic result at energies close to the dissociation
threshold E
f
. We therefore combine a harmonic oscillator
approximation for the transition state sum of states with
a full numerical determination of the reactant density of
states to give our RRKM expression for N P3-atom
chains:
k
RRKM=HO
E
N
z
HO
E E
q
anh
E
: 56
Total bond dissociation rate constants obtained using
RRK, RRKM and simulation with f = 0.02 and b = 1
are plotted as a function of energy E for N = 25 in
Fig. 13. To further examine the validity of the harmonic
and statistical approximations to the dynamical rate con-
stant, we plot the ratios of harmonic (RRK) to anharmonic
(hybrid RRKM) and anharmonic to simulation results as a
function of energy per degree of freedom, E/N, in Figs. 18
and 19, respectively.
The ratios of RRK to hybrid RRKM rate constants are
simply the ratios of harmonic and anharmonic reactant
densities of states. Fig. 18 shows that, while the discrepancy
between the RRK and RRKM rate constants grows with
the number of atoms N at xed energy per mode, e = E/
N, at constant total energy E the ratio of RRK and RRKM
rate constants approaches unity (harmonic limit) as N
increases. For example, for total energy E = 1 the ratios
are 3.24(N = 2), 2.46(N = 3), 2.12(N = 4) and 1.89
(N = 5). RRKM total dissociation rate constants com-
0.3 0.4 0.5 0.6 0.7
E
N
1.5
2
2.5
3
3.5
k
RRKM
k
sim
Fig. 19. Ratio k
RRKM
(E)/k
sim
(E) as a function of energy per mode, E/N,
for N = 2 (red), N = 3 (green), N = 4 (blue) and N = 5 (purple). (For
interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
0.3 0.4 0.5 0.6 0.7
E
N
2.5
3
3.5
4
4.5
k
RRK
k
RRKM
Fig. 18. Ratio k
RRK
(E)/k
RRKM
(E) as a function of energy per mode, E/N,
for N = 2 (red), N = 3 (green), N = 4 (blue) and N = 5 (purple). (For
interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
28 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
puted with an anharmonic reactant density of states are
within a factor of 2 of the simulation result. The ratio of
RRKM to simulation rate constant shows an overall
increasing trend with increasing E/N.
Finally, Fig. 20 shows the ratios (k
RRK
/k
RRKM
) and
(k
RRKM
/k
sim
) as a function of E/N, N = 25, for tethered
chains with potential parameters corresponding to model
polyethylene [74,75,51,76] and tensile force f = 0.02.
9. Summary and conclusions
In this work we have studied the bond dissociation
kinetics of tethered atomic (Morse potential) chains under
tensile stress. Our focus has been the nonstatistical aspects
of the dissociation kinetics and the role of anharmonicity.
Statistical theories of unimolecular dissociation rate con-
stants, both RRKM and RRK (harmonic appproximation)
have been applied to predict bond-dissociation rates as a
function of energy and tensile force. A fully anharmonic
version of RRKM theory is implemented using Monte
Carlo integration to determine reactant and transition state
phase space volumes as a function of energy. Comparison
of statistical predictions with dynamical dissociation rate
constants obtained using trajectory simulations for chains
with N = 25 atoms shows that, while the RRK approxi-
mation signicantly overestimates the dissociation rate,
the fully anharmonic RRKM theory is quite accurate.
The eects of anharmonicity are at least partly able to
rationalize discrepancies between trajectory results and
classical transition state theory noted previously [29].
For the two-atom chain, N = 2, we also carry out a
detailed examination of phase space structure using Poin-
care surfaces of section. We note that good agreement
between the RRKM and dynamical rate constants is
obtained despite the fact that the reactant phase space con-
tains a signicant fraction of relatively short-lived trajecto-
ries (as judged by the number of intersections with the
SOS). For the N = 2 chain, we also implement a novel
approach to the extraction of decay rate constants based
on the classical spectral theorem. This approach corrects
for the presence of invariant bound (nonreactive) regions
of reactant phase space, and yields total dissociation rates
in close agreement with dynamical simulation.
Our statistical predictions for chains with N P3 atoms
are obtained using a hybrid statistical theory involving a
harmonic approximation for motion in the transition state
for bond dissociation. Further exploration of the dynamics
in the vicinity of the transition state in multimode chains
along the lines of the recent work by Uzer and Jae
[102,103,105] would clearly be worthwhile, as would an
investigation of the applicability of the spectral theorem
approach.
Appendix A. Determining the reactant phase space volume
NE
For N = 2, the congurational projection of M
0
is the
union of the rectangular region and and adjacent triangular
region shown in Fig. 4. The shape of this region ensures
that phase points in the vicinity of transition states 1 and
2 are sampled appropriately while avoiding leakage of
sampled points into nearby exit channels.
For example, for f = 0.02 and b = 1 the line x
1
= 3.303
is taken to dene a suitable boundary between sampling
regions in the vicinity of transition states 1 and 2 (see
Fig. 4). The line x
2
= x
1
+ 2r
+ r
eq
dening transition
state 1 intersects this line at (3.303, 8.898). The phase space
sampling for the rectangular region is then
x
1
2 0; 3:303 A:1a
x
2
2 0; r
eq
r
z
A:1b
p
j
2
2E
max
_
;
2E
max
_
_ _
; j 1; 2; A:1c
while that for the triangular region is
x
2
2 0; 8:898 A:2a
x
1
2 3:303; x
2
2r
z
r
eq
A:2b
p
j
2
2E
max
_
;
2E
max
_
_ _
; j 1; 2: A:2c
The phase space region M
0
therefore has volume
0.3 0.4 0.5 0.6 0.7
E
N
2.5
3
3.5
4
4.5
5
k
RRK
k
RRKM
0.4 0.5 0.6 0.7
E
N
0.5
1.5
2
2.5
k
RRKM
k
sim
a
b
Fig. 20. (a) Ratio k
RRK
(E)/k
RRKM
(E) as a function of energy per mode E/
N for N = 2 (red), N = 3 (green), N = 4 (blue) and N = 5 (purple). (b)
Ratio k
RRKM
(E)/k
sim
(E) as a function of energy per mode E/N for N = 2
(red), N = 3 (green), N = 4 (blue) and N = 5 (purple). Morse parameters
correspond to model polyethylene. (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this
article.)
J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132 29
V
0
2
2E
max
_
_ _
2
3:303r
eq
r
z
1
2
8:8982r
z
r
eq
3:303
_
_ _
:
A:3
For N = 2 the phase space volume NE is tted to the
form
NE E
2
c
0
c
1
E . . .; A:4
For N P3, dim(M
0
) = 2N and the region M
0
is dened by
the following ranges of phase space coordinates:
x
j
2 x
j1
; x
j1
r
z
; j 1; . . . ; N A:5a
p
j
2
2E
max
_
;
2E
max
_
_ _
; j 1; . . . ; N: A:5b
with x
0
= 0. Hence for the reactant region of phase space,
V
0
2r
z
2E
max
p
N
, and the function NE is tted to the
form
NE E
N
c
0
c
1
E . . .; A:6
that is, harmonic oscillator phase space volume plus anhar-
monic corrections.
Appendix B. Sampling phase points on the energy shell
For N degrees of freedom, the phase space volume
element is
dz dxdp dx
1
dx
N
dp
1
dp
N
: B:1
Introducing polar coordinates in momentum space, this
becomes
dz dx
1
dx
N
p
N1
dpdx B:2
where dx is the associated angular volume element. For
N = 2, dx = d/, with 0 6 / 6 2p, while for N = 3,
dx = sinhdh d/, with 0 6 h 6 p and 0 6 / 6 2p. To spec-
ify phase points on the energy shell, we change variable
from p to E, using
oH
op
oT
op
p B:3
(setting all masses m = 1) to obtain
dz dx
1
. . . dx
N
p
N2
dEdx: B:4
On the energy shell, the (2N 1)-dimensional element of
hypersurface area dr dz|
H(z)=E
is therefore
dr dx
1
dx
N
p
N2
dx: B:5
The task is then to sample points distributed according to
the distribution function implied by (B.5) (see also
[106,28]).
B.1. N = 2 degrees of freedom
The situation for N = 2 dof is very straightforward. The
volume element is
dr
N2
dx
1
dx
2
d/: B:6
To sample phase points, we simply choose points uni-
formly in some region R of conguration space,
x x
1
; x
2
2 R. If V(x) 6 E, we determine the value of
the momentum magnitude p required to satisfy H = E.
Momentum components are then dened according to
p = (psin/, pcos/), with angle / chosen at random in the
interval 0 6 / 6 2p.
B.2. N P3 degrees of freedom
The volume element in this case is
dr dx
1
dx
2
dx
3
pdx: B:7
It is therefore necessary to weight momentum values
according to p rather than the natural 3D weighting p
2
.
To accomplish this we use a rejection method [99].
Points are sampled uniformly at random inside a region
Rof x = (x
1
,x
2
,x
3
) space. For any given energy E, there is a
maximum possible momentum magnitude P, which will be
determined by the value of the kinetic energy at the poten-
tial minimum. For any sampled point x, provided
V(x) 6 E, we determine the associated scaled momentum
magnitude,
g
p
P
; 0 6 g 6 1: B:8
Now choose a random number q between 0 and 1.
(1) If g < q, we reject the point.
(2) If g > q, we accept the point. Gaussian variates in 3D
are then used to compute a random orientation for
the momentum vector in 3D. If ^n is a randomly cho-
sen vector on the 2-sphere, the chosen phase point is
z x; p p^n gP^n.
Analogous rejection procedures are used for sampling
the energy shell for N > 3.
Let N
trial
be the number of sampled points satisfying
V(x) 6 E; this is the total number of points sampled on
the energy shell, some of which will be rejected as above.
Let the number of accepted points {z
k
} be N
accept
. The
average value of any property F(z) is then
hF i
k
F z
k
N
accept
B:9
where the sum is over accepted points.
Appendix C. Stable and unstable manifolds of the PODS
The rst step in computing the full nonlinear stable and
unstable manifolds W
s=u
of the PODS is determination of
the linearized manifolds, E
s
and E
u
, respectively [107].
The monodromy matrix M corresponding to one trip
around the unstable periodic orbit PODS
1
provides a line-
arized approximation to the iterated dynamics of a phase
point on the SOS displaced from the PODS by
Dz = (DX,DP),
30 J.N. Stember, G.S. Ezra / Chemical Physics 337 (2007) 1132
MDz
M
XX
M
XP
M
PX
M
PP
_ _
DX
DP
_ _
DX
0
DP
0
_ _
Dz
0
: C:1
To determine M we propagate the displaced phase points
Dz
DX
= (DX,0) and Dz
DP
= (0,DP) for one iteration of the
SOS mapping. If Dz
DX
and Dz
DP
evolve to Dz
0
and Dz
00
respectively under the mapping, then DX M
XX
= X
0
, DX
M
PX
= P
0
and DP M
XP
= X
00
, DP M
PP
= P
00
. The matrix
M thus obtained can then be diagonalized to obtain eigen-
values and eigenvectors.
For example, for E E
f
0:1, eigenvalues are
k
1
= 0.715, k
2
= 1.399 with corresponding stable and
unstable eigenvectors z
s
= (X
s
,P
s
) = (0.9808,0.1948) and
z
u
= (X
u
,P
u
) = (0.9808, 0.1948), respectively. The
determinant of M is 1.00006, verifying symplecticity (area
conservation) of the linearized dynamics [60] to within rea-
sonable numerical accuracy.
Points on the (nonlinear) manifolds W
u=s
are obtained
by propagating phase points close to the periodic orbit
on the respective linearized manifolds forwards/backwards
in time. To visualize W
u=s
, we select 1000 initial conditions
along short segments of E
s/u
close to the PODS and prop-
agate all these phase points either forward or backwards in
time. The resulting manifolds for E
f
0:1 are shown in
Fig. 8. The bound complex region can be dened to be
the phase space volume enclosed by these two manifolds
between the PODS and their rst intersection [79].
Appendix D. Computing average gap times
To calculate hti
1
(E), the average gap time for trajectories
exiting via transition state 1, initial coordinate values on
transiton state 1 are selected according to
n0 2 0; r
z
D:1a
X0 X
PODS
1
E; D:1b
where X
PODS
1
E is the average value of coordinate X for
PODS 1 at energy E. The initial momentum variable
P(t = 0) is selected in the range
P0 2
T0
_
;
T0
_
_ _
; D:2
where the kinetic energy is T(0) = E V(X(0),n(0)). The
momentum P(0) is then P0
4T0 P0
2
_
, where
the positive root is taken so that the trajectory will enter
the reactant region in negative time.
To calculate the average gap time hti
2
(E), we sample
x
1
(t = 0) and p
1
(t = 0) on transition state 2 by selecting ini-
tial coordinate values in the ranges
x
1
0 2 0; x
max
1
E; D:3a
x
2
0 x
PODS
2
2
E D:3b
where x
max
1
E is a suitably chosen maximum value of coor-
dinate x
1
, and x
PODS
2
2
E is the average x
2
value for
PODS
2
(E). We sample initial momenta according to
p
1
0 2
2T0
_
;
2T0
_
_ _
; D:4a
p
2
0
2T0 p
1
0
2
_
; D:4b
where T(0) = E V(x
1
(0),x
2
(0)). We select only the posi-
tive solution for p
2
(0) so that again our trajectories will
propagate into the reactant region in negative time.
For both average gap time calculations, the dissociation
criterion is that either Xt > X
PODS
1
E (reaction 1) or
x
2
t > x
PODS
2
2
E, x
1
t < x
max
1
E (reaction 2). For
channel i, we therefore compute the average gap time for
trajectories that, in forward time, enter the reactant region
from either transition state and exit only through transition
state i. For both calculations we integrate n
traj
= 10
4
trajec-
tories for energies E E
f
0:1; E
f
0:2; E
f
0:3; E
0:4; E
f
0:5 and E
max
. Each trajectory is integrated with
time step s = 10
1
s
0
for n
step
= 5 10
5
time steps or until
reaction has occurred. A negligible number of trajectories
fail to react within n
step
timesteps.
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