Computational Materials Science 20 (2001) 213±227

www.elsevier.com/locate/commatsci

Simulations of distribution functions for rod-like

macromolecules in linear ¯ow near solid surfaces
A. Hijazi, A. Khater *
Laboratoire PEC UPRES-A 6087, Universit
e du Maine, 72085 Le Mans France
Received 29 June 2000; received in revised form 13 September 2000; accepted 29 September 2000

Abstract
Brownian two-dimensional simulations are constructed to calculate the probability distribution functions (PDFs), for
_ rot ,
macromolecular rod-like particles in a ¯owing solution near solid surfaces. This is done for a wide range of a ˆ c=D
where c_ is the constant shear rate of the linear hydrodynamic ¯ow and Drot is the di€usion coecient for the molecular
Brownian rotational motion. The surface simulations are developed on the basis of bulk simulations that are in
agreement with the exact numerical solutions of the bulk Boeder di€erential equation (BDE). This procedure ensures an
appropriate limit for the surface simulations. Surface restitution is introduced for Brownian and hydrodynamic events
to develop an algorithm for the surface collisions of the macromolecules. The surface PDFs, given as a function of
spatial and angular co-ordinates, are calculated for the possible range of restitution coecients that model interactions
between molecular species and surface topographies. These PDFs are consistently concave in the depletion layer as is
physically expected. For small a or low ¯ow conditions, the surface spatial PDF are shown to be the result of a dynamic
balance between competing Brownian and hydrodynamic collisions restitution. For large a, the rod-like macromole-
cules are shown to be evacuated from the depletion layer by the dominant hydrodynamic collisions restitution. This is
consistent with experimental observations. The surface angular PDF for the depletion layer are also calculated, showing
marked di€erences from their bulk counterpart. Ó 2001 Elsevier Science B.V. All rights reserved.

1. Introduction determined by two competing forces, the ®rst a

The most widely used experimental technique
for the observation of rotational di€usion of
macromolecules in hydrodynamic ¯ow is that
corresponding to dynamic light scattering and to
birefringence [1±3]. The motion and average ori-
entations of macromolecules at dilute concentra-
tions in the bulk of a ¯owing solution are
*
Corresponding author. Tel.: +33-43-833297; fax: +33-43-
833518.
E-mail address: khater@aviion.univ-lemans.fr (A. Khater).
0927-0256/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 0 2 5 6 ( 0 0 ) 0 0 1 7 8 - 6
hydrodynamic force stemming from the shear
¯ow, and the other thermal originating from
Brownian rotational di€usion. Boeder [4] is the
®rst to have studied this problem from the theo-
retical point of view for rod-like macromolecules.
He suggested, without the use of the Langevin
formalism or the Fokker±Planck equation [5,6], an
ordinary di€erential equation in two dimensions
(2D) that governs the bulk probability distribution
function (PDF), P …h†, which describes the average
orientations of the macromolecules. This Boeder
di€erential equation (BDE) is derived in 2D in
the plane of the ¯ow, for rod-like particles of
214 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
negligible cross-sections. The angle h describes the
macromolecular orientations with respect to a
reference direction.
P 00 ‡ …a sin2 hP †0 ˆ 0:
A key normalised quantity for the study of the
_ rot , where c_ is
problem is a, which is the ratio c=D
the constant shear rate of the linear hydrody-
namic¯ow and Drot is the di€usion coecient for
the Brownian rotational motion of the rod. Dif-
ferent macromolecules in solvents have naturally
di€erent Drot , whereas the ¯ow is characterised by
_ As has been pointed out [4] a solution in
a given c.
closed form cannot be obtained for the BDE
equation. Boeder hence gave initially a series so-
lution valid for only small values of a, and also a
Taylor development for the high values of a. The
latter, however, su€ers from the absence of nec-
essary boundary conditions. Some improvements
have been made since, on the one hand to remove
restrictions on cross-sections of the macromole-
cules, and on the other to be able to consider the
di€usion in three dimensions [7±9]. These im-
provements, however, are limited to small values
of a.
The analytical solution of the BDE equation in
the bulk has been obtained in a recent work [10]
for a wide range of a. Special analytical as well as
numerical methods are developed in order to cal-
culate accurately the Boeder bulk PDF over sev-
eral orders of magnitude, 10ÿ4 6 a 6 108 , and the
mathematical nature of the BDE equation is re-
vealed as a singular perturbation problem when a
becomes larger than about 103 . Since turbulence
e€ects are known to take place for a P 104 for
macromolecules such as the polysaccharide chain
the analysis is generally con®ned to inferior values.
In this paper we present Brownian simulations
for the PDF in the vicinity of solid impenetrable
surfaces [5,11,12]. An analytical solution in this
region comparable to that in the bulk is too
complex since the mathematical problem of the
collisions of the macromolecules with the surface is
analytically intractable. The surface simulations
are hence constructed as an alternative approach,
and this is done by adapting the bulk simulations
[10] introducing an appropriate surface collisions
algorithm.
Some surface simulations in 2D have been
constructed previously in particular concerning the
Brownian movement of polymers in a linear ¯ow
[5], in plane Poiseuille ¯ow [11], and for the dis-
persion of rod-like particles in a shear ¯ow [12].
Since the numerical solutions of the BED equation
were unavailable previously, there has been an
absence in the literature of a comparison between
the bulk part of the simulations and these nu-
merical solutions. To control the surface simula-
tions, however, where one is often led to making
reasonable but unveri®able assumptions as regards
the surface collisions algorithm [5,11±13] we
compare initially the bulk simulations with the
numerical solutions of the BDE equation.
The subject of the Brownian dynamics of hard
macromolecular spheres in solutions has also been
studied previously. It is discussed extensively in a
recent work [14] where it is pointed out that hard
sphere dispersions have proven dicult to simulate
due to the singular nature of the hard sphere inter
particle potential. It has been proposed, however,
[15] that the overlap of particles be treated as
elastic collisions.
In Section 2 we introduce the method of
Brownian simulations via those constructed to
calculate the PDF, P …h†, in the bulk of a ¯owing
dilute solution. These are shown to be in agree-
ment with the numerical solutions of the BED
equation [10]. These solutions for the bulk serve
hence as a reference for our surface simulations. In
Section 3 we present a model for the surface sim-
ulations. These are constructed for the joint PDFs,
P …h; n†, as a function of h and also of the norma-
lised distance of the centre of mass of the rods
from the surface, n ˆ zc =L, where L is their com-
mon length. To treat the collisions between the
rod-like macromolecules and the solid surface the
notion of geometric restitution is introduced de-
veloping an appropriate collisions algorithm. Two
independent restitution coecients are introduced
to model the Brownian and the hydrodynamic
collisions. The terms Brownian and hydrodynamic
collisions imply, respectively, the collisions in-
duced by the Brownian movement and by the
hydrodynamic shear ¯ow. The simulation results
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
are presented for a variety of situations and con-
clusions are given in Section 4.
2. Simulations in the bulk
In this section the simulation method is intro-
duced to calculate the Boeder PDF, P …h†, in the
bulk of a ¯owing solution, where a 6ˆ 0. These
simulations are compared and shown to be in
agreement with the exact numerical solutions of
the BDE equation. This ensures the appropriate
bulk limit conditions for the surface simulations.
Since the Boeder PDF is periodic with a period
equal to p, as the rod-like particles are indistin-
guishable when oriented at h or h ‡ p, the simu-
lation results should satisfy the condition:
P …h† ˆ P …h ‡ p†: …
The simulations are shown to be consistent with
this condition.
The simulations are determined by both
Brownian and hydrodynamic forces acting on the
particles in the dilute solution. The hydrodynamic
forces tend to align the rod-like particles in the
direction of the shear ¯ow with an average angular
speed, w, given in [4] by
w ˆ c_ sin2 h: …
To simulate the e€ects of hydrodynamic forces
in a time interval Dt between successive simulation
events, n and n ‡ 1, we compute Dhhyd …n ‡ 1; n†,
the hydrodynamic rotation about the centre of
mass of the particles using the following algo-
rithm:
Dhhyd …n ‡ 1; n† ˆ h…tn‡1 † ÿ h…tn † ˆ c_ sin2 hDt: …
This Dhhyd is e€ectively a negative increment, since
the rod always follows the direction of the hy-
drodynamic ¯ow.
In contrast the Brownian forces in the bulk
create a di€usive rotational motion of the parti-
cles. The Brownian rotation variable
Dhrot …n ‡ 1; n† may be given from a random
Gaussian distribution. It is, however, more con-
venient to work with a simpli®ed random variable:
Dhrot …n ‡ 1; n† ˆ Dhrot ; …
215
where h ˆ 0 is parallel to the ¯ow direction which
is also parallel to the wall. h is taken as positive or
negative in the trigonometric sense, it is negative
for example in Fig. 2. The elementary rotations
ÿDhrot and ‡Dhrot are, respectively, clockwise and
anticlockwise from a given h…n† in the simulation.
The procedure of Eq. (4) is e€ectively an approx-
imation compared to the Gaussian distribution.
To satisfy the Brownian condition that the simu-
lation interval Dt  1=drot , where drot ˆ kB T =
‰Drot Icm Š, and Icm is the moment of inertia of the
rod-like particles about their centre of mass, we
have found that the domains of interest for the
Gaussian distribution are reduced in practice to
values that permit the above approximation,
where small values of Dhrot are improbable. Large
values of Dhrot are also improbable. Dhrot is ®xed
for a given statistical ensemble of simulation runs
1†
for any given a. An appropriate random number
generator is employed in the algorithm [16] to se-
lect random simulation events avoiding cumulative
errors. Using this procedure, Dt may be given as a
virtual di€usion variable:
Dh2rot ˆ 2Drot Dt; …5†
where Drot ˆ 3kB T ln…L=d†=pgs L3 is the coecient
of Brownian rotation di€usion [7], gs the viscosity
2† of the solvent, kB the Boltzman's constant, T the
absolute temperature, and d is the diameter of the
macromolecular rod-like particles, d  L.
Dt may be eliminated now from the algorithm.
This procedure avoids ambiguities that could arise
owing to the arbitrary choice of the simulation
time interval [5]. Eqs. (3) and (5) lead consequently
to the hydrodynamic algorithm component in the
3† form:
Dhhyd ˆ a sin2 h‰Dh2rot =2Š: …6†
In a simulation we typically chose L  880 nm,
and Dhrot  0:05 rad, which engenders reasonable
elementary hydrodynamic rotations for a 6 102 .
For relatively high a P 102 , the basic simulation
random variable Dhrot may be chosen smaller.
These values are sucient to construct viable sta-
tistics.
In Fig. 1 the Brownian simulations of the Boe-
4† der bulk PDF is given for a ˆ 100. The results are
216 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227

Fig. 1. The PDF, for the orientations of the macromolecular rod-like particles in a hydrodynamic ¯ow, are presented for a relatively
_ rot ˆ 100. The continuous curve denotes the numerical solution of the BDE
high value of the shear to rotational di€usion ratio, a ˆ c=D
for this PDF. The black dots with error bars are the simulation results.

obtained from 108 hydrodynamic and stochastic
events per simulation run in a statistical ensemble
of various runs. The black dots are the mean val-
ues over a given statistical ensemble and the error
bars are the maximum uncertainty per point in an
ensemble. These simulation results are compared
with the numerical solutions of the BDE equation
presented as the continuous curve in Fig. 1. The
Boeder bulk PDF and the Brownian simulations
are normalised to unity. Simulation results for a
wide range of a have been made [10] though not
presented here and are generally in agreement with
the BDE numerical solutions.
3. Model for simulations near a solid surface
Near a solid surface the dynamics of the rod-like
particles acquires a new reference, namely the
distance zc that separates their centre of mass from
the surface along the vertical. The solid surface is
assumed here to be impenetrable. Note that
n ˆ zc =L is a normalised distance.
In the bulk it is possible to neglect the Brownian
translation di€usion for dilute solutions, since this
has no statistical incidence on the PDF, P …h†. Near
a solid surface this translation di€usion contrib-
utes to determining the displacement of the parti-
cles from the bulk towards the surface and in the
opposite sense. It consequently contributes to the
establishment of stationary probability distribu-
tion functions in the neighbourhood of the surface.
Brownian di€usion in fact comprises both rotation
and translation di€usion. For dilute solutions of
the particles, it is possible to treat these processes
separately since the macromolecules are free from
particle±particle interactions that would otherwise
couple their rotation and translation di€usion. In
this approximation a new Brownian random
variable, Dzc;tr is introduced that displaces the
particle in either sense normal to the surface. We
eliminate the simulation time step variable again in
order to derive an expression for Dzc;tr as a func-
tion of the basic simulation variable Dhrot , namely:
L
Dzc;tr ˆ  jDhrot j: …7†
3
The factor L/3 in Eq. (7) comes from the ratio of
the Brownian translation and rotation di€usion
coecients [7].
When the rod-like macromolecules are near to a
surface, the Brownian and hydrodynamic forces
may cause the collisions of their extremities with
the surface. Very little information is available in
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
the literature concerning the nature and dynamics
of these collisions. In previous simulations that
attempt to treat this problem, two algorithms have
been tested [5]. The so-called naive algorithm, a
®rst attempt, treats these collisions by ignoring
them, where if a particle should penetrate the solid
surface the corresponding simulation con®gura-
tion is not accepted. A second improved algorithm
begins by estimating the random time at which a
collision takes place during a simulation time step
with the use of a complicated time bisection pro-
cedure. The particle is then left in the collision
con®guration when it gets to it, with one extremity
touching the surface, until a random event allows
it to move away in the remainder of the simulation
time step. The simulation results of this algorithm
are dependant on the choice of the time step
leading to di€erent results for di€erent time steps.
Further, some of the calculated surface PDF using
this algorithm are convex in the depletion layer
which is physically dicult to understand for a
random ¯uctuating process.
In other research domains the interaction of a
¯ux of molecules incident at thermal energies on a
solid surface is treated from a completely di€erent
point of view [17]. This type of work yields little
information that may be useful for the present
problem.
Fig. 2. The two limiting cases for collision restitution following a Brownian translation di€usion event, along the upper and lower
array of ®gures, respectively. For e ˆ 0, the rod stays at its touch angle and waits until the next event. For e ˆ 1, it comes back to its
initial con®guration.
217
To construct our simulations near a solid sur-
face, we introduce the notion of geometric resti-
tution for both Brownian and hydrodynamic
collisions. Since the nature of these collisions is
di€erent, random when arising from di€usion and
causal under the hydrodynamic shear, two sepa-
rate restitution coecients, e and e0 , are considered
to describe these collisions, respectively. The co-
ecient e is used to describe the collisions arising
from both the translation and the rotation di€u-
sions.
To illustrate the collisions algorithm, we present
in Fig. 2 a sequence of events, named n, ncollision ,
n ‡ 1, for a collision between a rod-like macro-
molecule and a solid surface, arising due to
translation di€usion. Near a surface the extremi-
ties, e1 and e2 , need to be distinguished in order to
follow the collision of one or the other with the
surface. The ambiguities arising from the simula-
tion time steps [5], where time is a continuous
variable, are eliminated here since we work with
Dhrot , a basic simulation random variable.
In Fig. 2 the two limiting cases that correspond
to e ˆ 0 and e ˆ 1 are presented along the upper
and lower array of ®gures, respectively. In the case
when a random translation di€usion event Dzc;tr
brings one of the extremities of the rod into colli-
sion with the surface, we may write that
218 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227

L L manner, where in this case zc …n ‡ 1† ˆ zc …n† is the

zcollision ˆ j sin h…n†j ˆ j sin h…n ‡ 1†j: …
2 2
h…n† ˆ h…n ‡ 1† is the touch angle. It is then pos-
sible to write the algorithm for the Brownian dif-
fusion translation between n and n ‡ 1, via a
collision, as
zc …n ‡ 1† ˆ zcollision ‡ e‰zc …n† ÿ zcollision Š: …
In a given simulation event the two limiting
cases, in Fig. 2, correspond, respectively, to a
Brownian translation di€usion that leaves the
colliding extremity momentarily at rest at the
surface for e ˆ 0 and to a geometric return to its
initial position for e ˆ 1. The next event moves the
particle into other con®gurations. For a given
macromolecular specie and a given topography of
the prepared surface [18,19] the collisions arising
due to random di€usion processes may be conse-
quently characterised by a given e coecient. A
comparable algorithm may be given for a collision
arising due to rotation di€usion, since these pro-
cesses are considered intrinsically similar.
The rotation di€usion that brings one of the
extremities of the particle into collision with the
surface may be characterised in a comparable
8† touch distance of the centre of mass from the
surface and
hcollision ˆ j arcsinfzc …n†=Lgj
ˆ j arcsinfzc …n ‡ 1†=Lgj: …10†
It is next possible to write the Brownian rotation
9† algorithm between n and n ‡ 1 events, via a colli-
sion, as
h…n ‡ 1† ˆ hcollision  ejhcollision ÿ h…n†j: …11†
The plus or minus sign depends on which of the
two extremities collides with the surface.
It is necessary next to construct an algorithm for
the hydrodynamic collisions. Using an indepen-
dent restitution coecient, e0 , the parameter in-
terval 0 6 e0 6 1 is considered to correspond to the
angular interval situated between hcollision (for
e0 ˆ 0), which is the surface touch angle for the
colliding extremity and p=2 (for e0 ˆ 1), a sup-
posed maximum that the particle can turn into
under the ¯ow. In the present analysis the colli-
sions arising due to the hydrodynamic ¯ow, for a
given macromolecular specie and a given topog-
raphy of the prepared surface, are characterised
by a given value of the e0 coecient. In Fig. 3 we

Fig. 3. The two limiting cases that correspond to collision restitution following a hydrodynamic rotation event, along the upper and
lower array of ®gures, respectively. For e0 ˆ 0, the rod stays at its touch angle corresponding to a sliding possibility under the ¯ow and
waits until the next event. For e0 ˆ 1, it turns into a maximum p=2 angle.
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227 219

illustrate the two limiting cases of e0 ˆ 0 and 1.
The interpretation that may be given to the limit-
ing case of e0 ˆ 0 is that for ideally smooth sur-
faces a colliding macromolecular rod-like particle
may slide under the ¯ow without turning. Al-
though a rare event, this has been observed in re-
cent experiments on microscopic polymer rod-like
particles in a ¯owing solution [20]. A mixture of
some sliding and turning is a more likely event for
surfaces with e0 6ˆ 0. It is also possible that the
maximum angle which the macromolecular rod-
like particles turn into, is greater than p=2. Recent
experiments [20] show an average maximum
turning angle of 3p=4. However, it is not known
whether these experiments scale down to the na-
nometric size macromolecules. Furthermore, the
polymer microscopic particles are too large to ex-
hibit random di€usion.
4. Simulation results and conclusions
To circumscribe the present uncertainty as re-
gards the topography of prepared solid surfaces in
these experiments, and the nature of the collision
between the extremity of a macromolecule and
the surface, the simulations are carried out for
di€erent values of e and e0 . They are also

Fig. 4. The simulation results for the normalised spatial PDF in the depletion layer and the bulk, calculated for relatively small a ˆ 2,
for di€erent restitution possibilities. The ®gures correspond to: (a) e ˆ 0, (b) e ˆ 0:3, (c) e ˆ 0:6, (d) e ˆ 1, where in each the hy-
drodynamic restitution is varied through e0 ˆ 0; 0:1; 0:3; 0:6; 1. The PDF are consistently concave in the depletion layer.
220 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227

presented for diverse values of a. The purpose is quantities that depend on these PDF and to
to calculate near a solid surface the stationary discern their tendencies for low and high ¯ow
PDF functions, P …h; n†, a number of measurable conditions.

Fig. 5. The simulated PDF, as in Fig. 4, calculated for relatively high a ˆ 200, for a typical Brownian restitution, e ˆ 0:6. The hy-
drodynamic restitution is varied through e0 ˆ 0; 0:3; 0:6; 1. The PDF are consistently concave in the depletion layer.

Fig. 6. The simulation normalised spatial PDF in the depletion layer, calculated for a solution at rest, a ˆ 0, for e ˆ 0, 0.5, 1, presented
as discrete results in comparison with the normalised arcsin function, itself presented as the analytic curve, which de®nes the theoretical
limit of the rod exclusion domain.
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227 221

These PDF are the stationary PDFs for the
particles, themselves in constant movement, com-
ing from the bulk of the ¯owing solution into the
neighbourhood of the surface then leaving the
depletion layer to go back into the bulk. To ensure
the conservation of the particle numbers in the
simulation, we con®ne the particles inside a space
between two comparable surfaces a distance D > L
apart. Unless otherwise speci®ed the simulations
are constructed for D ˆ 2L. Bulk conditions are
retrieved for n > 0:5. If and when a particle in the
simulation passes from one half into the other, it is
reintegrated into the initial half using appropriate
anti-symmetric conditions across the mid plane.

Fig. 7. The simulation results for the normalised spatial PDF, in the depletion layer and the bulk, as a function of a: (a) for relatively
small a where the concave PDF increase slightly with increasing a; (b) for relatively high a where the concave PDF decrease markedly
with increasing a.
222 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
Although the simulation results are presented as
a function of normalised parameters such as a and
n, it is convenient to work out the simulations
using typical variables as is done for the bulk. Dhrot
is considered hence as typically 0.05 rad, which
yields Dzc;tr  10ÿ2 L and as previously Dhhyd
 10ÿ3 a. For relatively high values of a P 102 , the
simulation random variable Dhrot is chosen small-
er. This range of values is sucient to construct
viable statistics.
In this section the normalised numerical results
are given for a variety of ¯ow conditions and
surface restitution coecients, in the form of the
projected PDF components. These are, respec-
tively,
Z p=2
P …n† ˆ P …h; n† dh …12†
ÿp=2
in the depletion layer and the bulk and
Z 1=2
Pdl …h† ˆ P …h; n† dn; …
0
in the depletion layer. Unless otherwise speci®ed,
the simulation results are obtained from 108 hy-
drodynamic and stochastic events per simulation
run. Since the order of magnitude for the error
Fig. 8. The simulation results for the surface excess function plotted as a function of a.
bars is known for a statistical ensemble, as seen in
Fig. 1 for example, the surface simulation results
are presented here without the corresponding error
bars.
In Figs. 4(a)±(d) simulation results are presented
for the normalised PDF P …n†, for the depletion
layer 0 6 n 6 0:5 as well as for the bulk, for the
relatively low ¯ow conditions a ˆ 2, and for four
values e ˆ 0, 0.3, 0.6, 1, respectively, as a function
of increasing e0 . This latter varies typically through
0, 0.1, 0.3, 0.6, 1, in each ®gure. These results il-
lustrate the variations of the concave PDF. These
show a dependence on the Brownian restitution e.
They are also seen for a ®xed e to decrease in the
depletion layer with increasing hydrodynamic
restitution e0 . This decrease is not linear and the
PDF seem to come to their concave minima
bunching together for e0 P 0:3. For small a, the
variations of the PDF with e and e0 are of a
comparable order of magnitude. For the sake of
comparison, the normalised simulation PDF for
13† high ¯ow conditions, a ˆ 200, are presented in
Fig. 5 this for a typical e ˆ 0:6 value. It is seen in
this case that the concave PDF also decrease with
increasing e0 . An interesting observation is that the
PDF are systematically concave in the depletion
layer for high and low ¯ow conditions. This is
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227 223

physically to be expected owing to the di€usive
nature of the Brownian movement as seen in
Fig. 6.
When the solution is at rest, a ˆ 0, the hydro-
dynamic collision restitution is absent, and our
surface simulations are constructed on the basis of
the Brownian collisions restitution only. In Fig. 6
we present the surface PDF simulation results for
this case for a range of values of the e coecient.
Two important conclusions may be drawn from
Fig. 6. Firstly, all the surface PDF simulation re-
sults lie above and do not cross the normalised
arcsin curve which de®nes the theoretical limit of
the rod-like exclusion domain. This con®rms the
validity of the surface simulations. To our
knowledge this is the ®rst time that a comparable
procedure is employed to test the surface simula-
tions. Secondly, the simulated surface PDF are
quite similar to the theoretical exclusion limit in
the complete interval 0 6 e 6 1. The simulated
surface PDF nearest to the theoretical limit cor-
responds to e ˆ 1.

Fig. 9. The simulation results for the normalised angular PDF in the depletion layer, as a function of a: (a) for relatively small a; (b) for
relatively high a.
224 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
In Fig. 7 the variation of the PDF with in-
creasing ¯ow conditions are presented for e ˆ 1
and e0 ˆ 1. This choice for the restitution coe-
cients is maintained in the rest of this work. As has
been pointed out e0 ˆ 1 seems to be a reasonable
choice judging by recent experiments [17]. A typi-
cal choice of e ˆ 1 also seems appropriate fol-
lowing Fig. 6, although a small error is introduced
in this case for small a and small e, near the de-
pletion layer boundary.
For relatively small a, as in Fig. 7(a), the sim-
ulation results show that the concave PDF P …n†
tends to increase modestly with increasing a in the
depletion layer. This may be explained as due to
the in¯uence of the Brownian compared to the
hydrodynamic collisions restitution for relatively
low ¯ow conditions. The Brownian restitution has
a tendency to induce a lingering e€ect for the
particles in the depletion layer once they arrive
from the bulk. For relatively high a, the hydro-
dynamic restitution is very active and supersedes
the in¯uence of the Brownian restitution. In this
case the concave PDF P …n†, decrease with in-
creasing a in the depletion layer going to a theo-
retical minimum of a Heaviside step function at
the boundary n ˆ 0:5, as may be seen in Fig. 7(b).
Physically, this implies that the increasing ¯ow rate
in the channel should evacuate the depletion layer
Fig. 10. The variation of hmaximum with a from the simulation results for the normalised angular PDF in the depletion layer. This
contrasts strongly with the variation of the same quantity in the bulk.
from its rod-like particles via hydrodynamic col-
lisions restitution for high a. The simulation results
for high a are consistent with observed experi-
mental data [3].
The variations of the projected spatial PDF,
P …n† with a, may be succinctly summarised via the
surface excess function. This is de®ned as
Z 1=2
1
Cˆÿ fPdl …n† ÿ Pb …n†g dn: …14†
0 Pb …n†
Pdl …n† and Pb …n† denote in Eq. (14) the spatial PDF
in the depletion layer and in the bulk, respectively.
The simulation results for the surface excess C are
presented in Fig. 8, as a function of a, for e ˆ 1
and e0 ˆ 1. In previous work [5] the question
whether C should increase or decrease has been
discussed, and is also shown to undergo a transi-
tion qualitatively comparable to that in Fig. 8. To
our knowledge, however, this is the ®rst time that a
clear behaviour is calculated as a function of a,
with a functional transition of C shown to take
place for a  15, for systematically concave and
hence physically acceptable PDF. The minimum
exists as a transition between Brownian and hy-
drodynamic dominated PDF events.
Up to this point we have presented simulation
results for the spatial PDF P …n†. In what follows
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227 225

simulation results for the angular PDF P …h† are function of the increasing a. The maximum angle
presented for the depletion layer. For e ˆ 1 and hmax of the bulk angular P …h† [10], varies strongly
e0 ˆ 1, we give these in Figs. 9(a) and (b) as a with the ¯ow, decreasing monotonically from a

Fig. 11. A comparison of the simulation results for the normalised angular PDF in the depletion layer and in the bulk, as a function of
a: (a) for relatively small a ˆ 5; (b) for relatively high a ˆ 200, ¯ow conditions.
226 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227

high 45°, for small a to much smaller angles for
a  104 . In contrast the maximum angle hmax for
the depletion layer angular PDF P …h† has quite a
di€erent variation with a as shown here in Fig. 10.
To illustrate the di€erence of the depletion layer
PDF P …h†, in comparison with the bulk PDF P …h†,
we present both in Figs. 11(a) and (b) for, re-
spectively, low a ˆ 5 and high a ˆ 200, ¯ow con-
ditions. Note the narrowing of both PDF for the
high ¯ow conditions, which is expected, as the ¯ow
tends to increasingly align the rod like particles in
the direction of the ¯ow.
The simulations can also yield the angular PDF
P …h† at di€erent planes n inside the depletion layer.

Fig. 12. The variation of the simulation results for the normalised angular PDF calculated for di€erent planes inside the depletion
layer: (a) for relatively low a ˆ 2; (b) for relatively high a ˆ 200; ¯ow conditions.
 A. Hijazi, A. Khater / Computational Materials Science 20 (2001) 213±227
To illustrate this we present these planar angular
PDF P …h†, for low a ˆ 2 and high a ˆ 200, ¯ow
conditions, in Figs. 12(a) and (b), respectively. In
each of these ®gures the results are presented for
the planes n ˆ 0:1; 0:2; 0:3; 0:4; and are normalised
with respect to the global angular PDF inside the
depletion layer, at a given a. The planar angular
PDF P …h† are observed to drop rapidly to zero at
the rod-like exclusion angle for the plane consid-
ered, as is expected. In Fig. 12(a) for the low a ˆ 2
¯ow conditions, the anti-symmetry of the angular
PDF P …h† for the planes away from the surface
and near the depletion layer boundary, comes
from the greater liberty exercised by the hydro-
dynamic restitution compared to the Brownian
restitution. This liberty of turning the rod in the
sense of the ¯ow is constrained for the planes near
the solid surface where the random di€usion
mechanism becomes more dominant. At the high a
¯ow conditions, this e€ect persists, as seen in
Fig. 12(b), but is modulated with a tendency to
narrow the PDF, as is observed in Fig. 11(b) for
the global angular PDF.
Acknowledgements
The authors should like to thank C. Tannous,
L. Auvray, T. Nicolai, J.-C. Gimel, J.-F. Tassin,
D. Durand, and D. Aussere for useful discussions.
227
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