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Disappearance of oscillations in the Brusselator on the mesoscopic

scale

Vladimir P. Zhdanovab

a Department of Applied Physics, Chalmers University of T echnology, 412 96 GoŽ teborg, Sweden.
E-mail : zhdanov=fy.chalmers.se
b Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk 630090, Russia.
E-mail : zhdanov=catalysis.nsk.su

Received 3rd January 2001, Accepted 14th February 2001

Published on 14 March 2001. Downloaded by Northeastern University on 23/10/2014 21:13:17.

First published as an Advance Article on the web 14th March 2001

The Brusselator is a classical model predicting kinetic oscillations in chemical reactions. Using a lattice version
of this model, we show by employing Monte Carlo simulations how due to Ñuctuations the periodic
oscillations may Ðrst become aperiodic and then disappear with decreasing system size.

1. Introduction 2. Model
Kinetic oscillations, chaos and pattern formation have long As an example, we treat the Brusselator,1,16
attracted attention of chemists, physicists and biologists.1h5
Traditionally, these phenomena are described by using the A]B (1)
reactionÈdi†usion (RD) equations based on the mass-action A ] C, (2)
law3h5 (MAL). With decreasing the system size down to the
mesoscopic scale (likely examples are cells or nm-supported 2A ] B ] 3A, (3)
catalyst particles), this approach, ignoring Ñuctuations, may D ] A, (4)
fail.
To include Ñuctuations into the scenairo, one can introduce with the imposed D concentration.
Gaussian white noise into the MAL or MAL-RD equations The conventional MAL equations corresponding to the
(see, e.g., refs. 6 and 7, respectively). The applicability of this scheme above are as follows,
strategy is however open for discussions because under the dc /dt \ k c2 c ] k [ k c [ k c , (5)
chemically reactive conditions the noise may be non- A 3 A B 4 1 A 2 A
Gaussian. Another option is to employ the master equations dc /dt \ k c [ k c2 c , (6)
B 1 A 3 A B
describing di†usion and reaction.8 The shortcoming of the where c and c are the A and B concentrations, and k , k ,
latter approach is that such equations often cannot be solved A B 1 2
k and k the rate constants corresponding to steps (1)È(4) (the
accurately. Alternatively, one can use the molecular dynamics, 3 4
D concentration is included into k ).
Monte Carlo (MC), or lattice-gas automata (LGA) techniques. 4
In our study, the reaction under consideration is assumed
The former method, based usually on the hard-sphere to run on a circular spot at a square lattice. Sites on the spot
models,9 is appropriate for gas-phase reactions. The latter two are either vacant or occupied by single A or B particles. C
(MC and LGAT) strategies resting customarily on the lattice particles are removed from the lattice immediately after exe-
models are aimed at reactions occurring at the interface or in cuting step (2). The A formation (4) is considered to occur on
condensed media. For example, we may mention the LGA vacant sites (this means that the D particles are not treated
studies of the Selkov and Maginu models (see the com- explicitly). A and B particles are allowed to di†use by jumping
prehensive review by Boon et al.10) and MC simulations of to nearest-neighbour (nn) vacant site. The rates of steps (1)È(4)
the kinetics of the model LotkaÈVolterra reaction11,12 and of are characterized by the normalized (O1) probabilities, p , p ,
the NOÈH and NOÈCO reactions on Pt(100).13,14 1 2
2 p and p , proportional to the corresponding rate constants.
The main goal of the available LGA and MC simulations of 3 4
In addition, we introduce the probabilities pd and pd of A and
kinetic oscillations was to reproduce the behaviour of macro- A B
B di†usion jumps.
scopic systems on the mesoscopic scale. Practically, this means
that the calculations were executed on rather large lattices 3. Algorithm of simulations
[from (100 ] 100) to (1000 ] 1000)] with periodic boundary
conditions. The other boundary conditions were used in MC The algorithm of MC simulations consists of trials to realize
simulations15 of oscillatory regimes of catalytic reactions one of the elementary processes on the spot. A site on the spot
occurring on nm-sized crystallites. The latter studies focused (site 1) is chosen at random. Then, a random number o (o O 1)
on the interplay of reactions run on di†erent facets of catalyst is generated and one of the elementary steps is executed as
particles. In both cases, the evolution of oscillations with follows :
decreasing lattice size was not illustrated in detail. (1) If site 1 is vacant, an A particle is created there provided
The present study focuses on a truly mesoscopic system (no that o O p .
4
periodic boundary conditions). SpeciÐcally, we show how Ñuc- (2) If site 1 is occupied by B, one of the nn site (site 2) is
tuations result in the disappearance of periodic oscillations chosen at random. If site 2 is located outside the spot, the trial
with decreasing system size. ends. If site 2 is on the spot, there are three options. (i) If site 2

1432 Phys. Chem. Chem. Phys., 2001, 3, 1432È1434 DOI : 10.1039/b100192m

This journal is ( The Owner Societies 2001
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is vacant, B is replaced to the latter site provided that o O pd .
B
(ii) If site 2 is occupied by B, the trial ends. (iii) If site 2 is
occupied by A, the third site is selected [see the insert in Fig.
1(e)] and if the latter site is located on the spot and occupied
by A step (3) is performed provided that o O p . Otherwise,
3 B
the trial ends.
(3) If site 1 is occupied by A, step (1), (2) or A di†usion are
executed provided that o O p , p O o O p ] p and p
1 1 1 2 1 B
] p O o O p ] p ] pd , respectively. [Note that here there
2 1 2 A
is no need to realize step (3) because the latter step occurs
when we choose B particles.] For A di†usion, one of the nn
site (site 2) is chosen at random. If site 2 is located outside the
spot, the trial ends. If site 2 is on the spot, A is replaced to the
latter site provided that it is vacant.
Initially (at t \ 0), the spot was free of reactants. After each
Published on 14 March 2001. Downloaded by Northeastern University on 23/10/2014 21:13:17.
To generate oscillations on the spot, the A and B concentra-
tions (per site) should be appreciable but far from saturation.
This means that we should have p A p . In addition, it is
1 4
desirable to have rapid A and B di†usion, i.e., pd A p and
A 1
pd A p . Following this guideline, we use p \ 5 ] 10~3, p \
1 1 2
10~3, p \ 0.5 and p \ 5 ] 10~5, pd \ 1 [ p [ p and
3 4 A 1 2
pd \ 1. (Note that p ] p @ 1 and accordingly pd is nearly
B 1 2 A
equal to pd.) The spot diameter, L , was changed from 100
down to 10.
4. Results of simulations
The results obtained in our simulations are shown in Figs. 1
and 2. For comparison, we have also calculated the MAL
kinetics (Fig. 3) by employing eqns. (5) and (6) with the dimen-

trial, the MC time was incremented by17 *t \ o ln(m) o/N , sionless rate constants equal to the MC rate probabilities (i.e.,
MC s
where m O 1 is a random number, and N the number of sites k \ 5 ] 10~3, k \ 10~3, k \ 0.5 and k \ 5 ] 10~5). In
s 1 2 3 4
on the spot. On average, we have S o ln(m) o T \ 1. Thus, this case, the MC and MAL kinetics can be compared
*t \ 1 corresponds to one trial per site or, in other words, directly, because the MC time exactly corresponds to real
MC
to one MC step (MCS). time.

Fig. 1 Numbers of A and B particles as a function of time during reaction on the spot with L \ 100 (a), 50 (b), 30 (c), 20 (d) and 10 (e). The insert
on panel (e) explains the rules for simulation of the 2A ] B ] 3A reaction. If site 1 is occupied by B (open circle), one of the nn site (e.g., site 2) is
chosen at random. If site 2 is occupied by A (plus sign), the third site (3 or 4) is selected at random. The reaction trial is considered to be successful
(i.e., A located in site 1 is replaced by B) if the latter site (e.g., site 3) is occupied by A as well.

Phys. Chem. Chem. Phys., 2001, 3, 1432È1434 1433

Published on 14 March 2001. Downloaded by Northeastern University on 23/10/2014 21:13:17.
Fig. 2 Snapshots of the spot with L \ 100 for the run, shown in Fig.
1(a), in the cases when the numbers of A and B particles are maximum
(at t \ 90 ] 103 and 91 ] 103 MCS, respectively). Plus signs and
open circles indicate A and B particles The sites outside the spot are
represented by Ðlled circles.
For L \ 100 [Fig. 1(a)], the MC kinetics are nearly periodic
in good agreement with the MAL prediction (Fig. 3) despite
appreciable Ñuctuations in the arrangement of reactants (Fig.
2). With decreasing L down to 50 and 30 [Fig. 1(b) and (c)],
the Ñuctuations in the the amplitude of oscillations increase
but the periodicity is still maintained (note that the average
period of oscillations becomes longer). For L \ 10 [Fig. 1(e)],
the system exhibits a few oscillations and then (at
1434 Phys. Chem. Chem. Phys., 2001, 3, 1432È1434
View Article Online
Fig. 3 A and B concentrations as a function of time according to
eqns. (5) and (6). (DU means dimensionless units.)
t [ 80 ] 103 MCS) is trapped in the unreactive state with all
the sites occupied by B. (For larger spots, the system may in
principle be trapped to this state as well but with increasing
spot size the probability of this event rapidly becomes negligi-
bly low.)
5. Conclusion
In summary, our simulations explicitly demonstrate that with
decreasing system size the periodic kinetic oscillations may
Ðrst become aperiodic and then disappear.
Acknowledgements
The author thanks B. Kasemo for useful discussions. The
Ðnancial support for this work was obtained from the
Waernska Guest Professorship Fund at GoŽteborg University.
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