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polyampholytes
Y. Rabin*+, ++, S. Panyukov++, m and M. Wilhelm+++, mm
+
Yukawa Institute for Theoretical Physics, Kyoto University, Kyoto 606-01, Japan
Department of Physics, Bar-Ilan University, Ramat-Gan 52900, Israel
+++
Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel
m
On leave from: Theoretical Department, Lebedev Physics Institute, Russian Academy of Sciences, Moscow 117924, Russia
mm
On leave from: Max-Planck-Institut fur Polymerforschung, D-55021 Mainz, FRG
++
We study the interaction between randomly and irreversibly charged rigid objects. We consider arbitrary parallel displacements of two rod-like polyampholytes and of two plates and calculate the statistical properties of the resulting energy landscape, such as the distribution of energy minima and the depth, width and density of typical energy wells, as a function of the
separation between the objects and of the Debye screening length. The possibility that stickslip phenomena may arise during relative motion of the objects is discussed. Other cases considered in this work are that of random distribution on one rod
and a periodic one on the other, and that of local periodic order on both rods.
1. Introduction
The statistical physics of interacting manybody systems deals with a thermodynamically large number of elementary units (atoms, spins, etc.), each of which is
described by a small number of parameters. This leads to a
class of models in which complex physical behavior arises
due to cooperative behavior of a large number of such
simple units. There is, however, a different class of interacting complex systems, of the type encountered in biology, in which the number of parameters necessary to specify a single unit (e. g., a protein) is very large. Due to the
inherent complexity of the individual units, even a small
number of such interacting objects can exhibit very complex behavior.
In this work we investigate a generic model of the latter
type, i. e., that of two interacting rigid objects on which a
random distribution of charges is irreversibly placed. Such
objects are extremely complex in the sense that complete
specification of the charge distributions requires precise
information about the location of each of the charges, the
number of which can be arbitrary large, depending on the
size of the objects. We allow for charges of both signs and
the resulting combination of long-range attractive and
repulsive forces leads to the appearance of complex interaction energy landscapes. We would like to stress that our
model differs from that of usual polyampholytes (i. e.,
polymers carrying charges of both signs) since we assume
that the charged objects are rigid and therefore both the
charge distribution and the conformation are quenched.
Recall that all polyampholyte models to date deal with
flexible polymers [1] and consider the thermal fluctuations
and the associated entropic elasticity of the polymer
chains.
In Sec. 2 we study the statistical properties of the interaction energy landscape of two parallel rod-like polyampholytes, on which positive and negative charges were randomly and irreversibly placed. The detailed derivation of
these results was presented in [2]. New results are derived
Fax: +972-3-535 3298
E-mail: yr@rabinws.ph.bin.ac.il
544
Acta Polym. 1998, 49, 544 548 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 1998
0323-7648/98/1010-0544$17.50+.50/0
dE dEuhw2 dEu=wu2
extr
where the sum goes over the positions u of all the energy
extrema for which wdEu=wu 0 and the h-function
ensures that only minima are counted (w2 dEu=wu2 A 0).
For two parallel rods, u is a scalar and w2 dEu=wu2 is the
inverse squared radius of curvature of the energy minimum, which is a measure of the stiffness of the potential
Fig. 2. Plot of the number of minima per unit energy per unit
length, Nmin E=L9 , as a function of their energy dE , for different
vertical separations between the rods. The broken line corresponds
to h L and the solid line to h 0:1L (with g 1).
L9
p pmin y
g hL
where
p
y2
y2
2
pmin y 3
exp
5 exp
16p2
2p
25p
y erf
y
p
5 p
and
E
y3
g
y
r
h
L
545
Another important result is the dependence of the stiffness of the average potential well, K w2 dEu=wu2 , on
the distance h between rods,
Kh Kh0 m2 h=m2 h0 1=2
Equation (7) shows that the distribution of the radii of curvature of the energy minima is invariant with respect to the
change of the distance between rods. Thus, when the two
rods approach each other, existing minima become progressively stiffer and deeper, just as in the case of rods with
charges that form a regular periodic lattice. At the same
time, new shallow minima appear and grow in depth as h is
reduced. The appearance of new minima is a characteristic
signature of random charge distributions on the rods and
has no analog in the periodic case, i. e., when the frozen
charge distributions on both rods are periodic, with the
same period k. In the latter case, the number of minima is
independent of the distance between the rods, and their
depth increases monotonically with decreasing separation
h.
Our main analytical results for the unscreened Coulomb
case can be rederived by a simple scaling estimate. Let us
replace the microscopic charge distribution by one that is
coarse-grained over a length scale h (the distance between
the rods). Each electrostatic blob contains gh charges of
both signs and thus the total charge per blob is of order
Qh lgh1=2 . Since there are L=h such blobs and the
average interaction energy between the rods vanishes
(assuming that there is no net charge on the rods), dE can
written as the sum of interaction energies of L=h neighboring blobs on the two rods. Each one of the contributions is
a random function, which takes the values lQ2h =h, and
therefore the total interaction energy is also a random
quantity with zero average and characteristic deviation
dE x l L=h1=2 Q2h =h l gL=h1=2 , in agreement with
the exact result, Eq. (5).
We study the interaction energy landscape for two parallel rods: rod 2 is of length L9 with a randomly frozen density distribution q2 and rod 1 is of length L (L s L9 ) with a
frozen periodic density distribution
dq1 x qeiqx q eiqx ;
q 2p=d
x9
dke
R
dq2 x dk9eik9x dqk9 , the interaction energy can be
written as Eu
Eu Vq dqq qeiqu Vq dqq q eiqu
The calculation of the average number of minima is performed using the method described in [2] and the resulting
expression for Nmin is very similar to that in Eq. (19) in the
above reference,
Acta Polym. 1998, 49, 544 548
Zv
Nmin E L
3 Z
Y
dkj
dKK
6
2p
j1
"
2
#
Djl kj kl
10
jl
with
mi q2i jVq j2
12
15
dEmin is a function both the wavelength 2p=q and the distance between the rods, h. Obviously, this expression
vanishes in the limit jh S 1 (strong screening). In the
opposite limit, jh s 1 (no screening), we have to distinguish between the cases qh S 1,
s
2p qh
e
Vq x
qh
and qh s 1, for which
Vq x 2 lnqh
Since, in the case of random charge distributions on
both
p
rods, the depth of a typical minimum is dEmin V g L=h,
we conclude that for g h s 1this depth is larger in the randomperiodic case than in the randomrandom case.
Another difference between the two cases is that the number of such typical energy minima is independent of the
distance between the rods in the randomperiodic case and
decreases with the separation in the randomrandom case.
Acta Polym. 1998, 49, 544 548
q 2 p=d
jx x9j
rc
2p x x9
cos
d
jxx9j=rc
p
dEmin L q2 rc LjVq j
3. Parallel plates
547
parallel to it. If the distribution of charge on the plates is uniform, there will be no restoring forces associated with this
displacement and consequently plate 2 will not move. The
presence of frozen random charge distributions on the plates
leads to the appearance of a large number of energy minima,
which correspond to different relative parallel displacements of the plates. Since, for macroscopic plates, the typical energy associated with these minima scales as A1=2 , for
sufficiently large plates it may become much larger that the
thermal energy kB T and the plates will get stuck in one of
the minimal energy configurations. Plate 2 will move
together with plate 1 (stick phase) until the force on it
exceeds some critical value fcrit , at which point it will recoil
back (slip phase). This value can be estimated from the characteristics of the typical energy well and for h f j1 we
obtain fcrit x gA1=2 =h. At larger distances, screening comes
into play and this force decays exponentially with separation between the plates (no stick phase is expected at large
separations). Conversely, the stickslip phenomenon can
be suppressed by the addition of salt, even when the separation between the plates is fixed.
When the critical force is exceeded, plate 2 will recoil
back to a position in which the spring force becomes sufficiently small. The process will repeat itself as long as we
continue to drag plate 1, and stick-slip motion of plate 2
will be observed. Note that each time the critical spring
force is exceeded, plate 2 recoils to a different new equilibrium state, which corresponds to an energy minimum that
differs in general from the initial one (such minima are
densely distributed in the space of relative displacements
of the two plates) and, therefore, a statistical spread of
equilibrium positions of the lower plate will result.
4. Discussion