biophysical chemistry of biointerfaces (ohshima/biophysical chemistry of biointerfaces) || potential...
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2 Potential Distribution Around aNonuniformly Charged Surfaceand Discrete Charge Effects
2.1 INTRODUCTION
In the previous chapter we assumed that particles have uniformly charged hard sur-
faces. This is called the smeared charge model. Electric phenomena on the particle
surface are usually discussed on the basis of this model [1–4]. In this chapter we
present a general method of solving the Poisson–Boltzmann equation for the elec-
tric potential around a nonuniformly charged hard surface. This method enables us
to calculate the potential distribution around surfaces with arbitrary fixed surface
charge distributions. With this method, we can discuss the discrete nature of
charges on a particle surface (the discrete charge effects).
2.2 THE POISSON–BOLTZMANN EQUATION FOR A SURFACEWITHAN ARBITRARY FIXED SURFACE CHARGE DISTRIBUTION
Here we treat a planar plate surface immersed in an electrolyte solution of relative
permittivity er and Debye–Huckel parameter k. We take x- and y-axes parallel to theplate surface and the z-axis perpendicular to the plate surface with its origin at the
plate surface so that the region z> 0 corresponds to the solution phase (Fig. 2.1).
First we assume that the surface charge density s varies in the x-direction so that sis a function of x, that is, s¼ s(x). The electric potential c is thus a function of xand z. We assume that the potential c(x, z) satisfies the following two-dimensional
linearized Poison–Boltzmann equation, namely,
@2
@x2þ @2
@z2
� �cðx; zÞ ¼ k2cðx; zÞ ð2:1Þ
Equation (2.1) is subject to the following boundary conditions at the plate surface
and far from the surface:
@cðx; zÞ@z
����z¼0
¼ � sðxÞereo
ð2:2Þ
Biophysical Chemistry of Biointerfaces By Hiroyuki OhshimaCopyright# 2010 by John Wiley & Sons, Inc.
47
and
cðx; zÞ ! 0;@c@z
! 0 as z ! 1 ð2:3Þ
To solve Eq. (2.1) subject to Eq. (2.3), we write c(x, z) and s(x) by their Fourier
transforms,
cðx; zÞ ¼ 1
2p
Zcðk; zÞeikx dk ð2:4Þ
sðxÞ ¼ 1
2p
ZsðkÞeiks dk ð2:5Þ
where cðx; zÞ and sðkÞ are the Fourier coefficients. We thus obtain
cðk; zÞ ¼Zcðx; zÞe�iks dx ð2:6Þ
sðkÞ ¼ZsðxÞe�ikx dx ð2:7Þ
Substituting Eq. (2.4) into Eq. (2.1) subject to Eq. (2.3), we have
@2cðk; zÞ@z2
¼ ðk2 þ k2Þcðk; zÞ ð2:8Þ
which is solved to give
cðk; zÞ ¼ CðkÞexpð�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞ ð2:9Þ
x
y
z
O
FIGURE 2.1 A charged plate in an electrolyte solution. The x- and y-axes are taken to be
parallel to the plate surface and the z-axis perpendicular to the plate.
48 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
where C(k) is the Fourier coefficient independent of z. Equation (2.4) thus becomes
cðx; zÞ ¼ZCðkÞexp½ikx� z
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p�dk ð2:10Þ
The unknown coefficient C(k) can be determined to satisfy the boundary condition
(Eq. (2.2)) to give
CðkÞ ¼ sðkÞereo
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p ð2:11Þ
Substituting Eq. (2.11) into Eq. (2.10), we have
cðx; zÞ ¼ 1
2pereo
ZsðkÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p exp ikx�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pz
h idk ð2:12Þ
which is the general expression for c(x, z).Consider several cases of charge distributions.
(i) Uniform smeared charge density Consider a plate with a uniform surface
charge density s
sðxÞ ¼ s ð2:13Þ
From Eq. (2.7), we have
sðkÞ ¼ sZexpð�ikxÞdx ¼ 2psdðkÞ ð2:14Þ
where d(k) is Dirac’s delta function and we have used the following rela-
tion:
dðkÞ ¼ 1
2p
ZexpðikxÞdx ð2:15Þ
Substituting this result into Eq. (2.12), we have
cðx; zÞ ¼ sereo
ZdðkÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p exp ikx�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pz
h idk ð2:16Þ
Carrying out the integration, we obtain
cðzÞ ¼ sereok
e�kz ð2:17Þ
THE POISSON–BOLTZMANN EQUATION FOR A SURFACE 49
which is independent of x and agrees with Eq. (1.25) combined with
Eq. (1.26), as expected.
(ii) Sinusoidal charge distribution Consider the case where the surface charge
density s(x) varies sinusoidally (Fig. 2.2), namely,
sðxÞ ¼ cosðqxÞ ð2:18ÞFrom Eq. (2.7), we have
sðkÞ ¼ZcosðqxÞe�ikx dx
¼ 1
2
Zðeiqx þ e�iqxÞe�ikx dx
¼ s2ð2pÞ dðk þ qÞ þ dðk � qÞf g
ð2:19Þ
Substituting this result into Eq. (2.12), we have
cðx; zÞ ¼ s2ereo
Zdðk þ qÞ þ dðk � qÞf gffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
k2 þ k2p exp ikx�
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pz
h idk
¼ s2ereo
1ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ q2
p exp iqx�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiq2 þ k2
pz
h iþ exp �iqx�
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiq2 þ k2
pz
h i
¼ sereo
cosðqxÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ q2
p exp �ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiq2 þ k2
pz
h ið2:20Þ
When q¼ 0, Eq. (2.20) reduces to Eq. (2.17) for the uniform charge distri-
bution case. Figure 2.3 shows an example of the potential distribution
c(x, z) calculated from Eq. (2.20). It is to be noted that comparison of Eqs.
(2.20) and (2.18) shows
cðx; zÞ ¼ sðxÞereo
exp½�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiq2 þ k2
pz�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
k2 þ q2p ð2:21Þ
FIGURE 2.2 A plate surface with a sinusoidal charge distribution.
50 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
That is, in this case the surface potential c(x, z) is proportional to the sur-
face charge density s(x).The surface potential c(x, 0) calculated from Eq. (2.20) is given by
cðx; 0Þ ¼ sereo
cosðqxÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ q2
p ð2:22Þ
which is a function of x.
(iii) Sigmoidal distribution We treat a planar charged plate with a gradient in
surface charge density, which is s1 at one end and s2 at the other, varying
sigmoidally between s1 and s2 along the plate surface [5] (Fig. 2.4). We
may thus assume that the surface charge density s varies in the x-directionaccording to the following form:
sðxÞ ¼ s1 þ s2 � s11þ expð�bxÞ
¼ 1
2ðs1 þ s2Þ þ 1
2ðs2 � s1Þtanh bx
2
� � ð2:23Þ
where b(�0) is a parameter proportional to the slope of s(x) at x¼ 0.
An example of charge distribution calculated for several values of b/k at
FIGURE 2.3 Scaled potential distribution c�(x, z) =c(x, z)/(s/ereok) around a surface witha sinusoidal charge density distribution s(x) = s cos(qx) as a function of kx and kz, where kxand kz are the scaled distances in the x and y directions, respectively. Calculated for q/k = 1.
THE POISSON–BOLTZMANN EQUATION FOR A SURFACE 51
s2/s1¼ 3 is given in Fig. 2.5. From Eq. (2.7), we have
sðkÞ ¼ 1
2ðs1 þ s2ÞdðkÞ � iðs2 � s1Þ
b sinhðpk=bÞ� �
ð2:24Þ
Then by substituting Eq. (2.23) into Eq. (2.12), we obtain the solution to
Eq. (2.1) as
cðx; zÞ ¼ ðs1 þ s2Þ2ereok
e�kz þ ðs2 � s1Þbereo
Z 1
0
expð�kzffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
p ÞsinðkxtÞffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
psinhðpkt=bÞ dt ð2:25Þ
FIGURE 2.4 A plate surface with a sigmoidal gradient in surface charge density. The
surface charge density s varies in the x-direction. s(x) tends to s1 as x!�1 and to s2 asx!+1, varying sigmoidally around x= 0. From Ref. 5.
FIGURE 2.5 Sigmoidal distribution of reduced surface charge density s�(x), defined by
s�(x) = 2s(x)/(s1 +s2), as a function of kx for several values of b/k at s2/s1 = 3. The limiting
case b/k=1 corresponds to a sharp boundary between two regions of s1 and s2. The oppo-site limiting case b/k = 0 corresponds to a uniform charge distribution with a density
(s1 + s2)/2. From Ref. 5.
52 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
which gives the potential distribution c (x, z) around a charged plate
with a sigmoidal gradient in surface charge density given by Eq. (2.23)
as a function of x and z. The first term on the right-hand side of Eq.
(2.25) corresponds to the potential for a plate carrying the average
charge of s1 and s2. Equation (2.25) corresponds to the situation in
which there is no flow of electrolyte ions along the plate surface, al-
though a potential gradient (i.e., electric field) is formed along the plate
surface. The potential gradient is counterbalanced by the concentration
gradient of electrolyte ions. The electrochemical potential of electrolyte
ions thus takes the same value everywhere in the solution phase so that
there is no ionic flow.
To calculate the potential distribution via Eq. (2.25), one needs numeri-
cal integration. Figure 2.6 shows an example of the numerical calculation of
c(x, z) for b/k¼ 1 at s2/s1¼ 3. As will be shown later, the potential c(x, z)is not always proportional to the surface charge density s(x) unlike the casewhere the plate is uniformly charged (s¼ constant).
We now consider several limiting cases of Eq. (2.25).
(a) When b=k � 1, Eq. (2.25) tends to the following limiting value:
cðx; zÞ ¼ s1 þ s22ereok
expð�kzÞ þ 2ðs2 � s1Þpðs1 þ s2Þ
Z 1
0
expð�kzffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
p ÞsinðkxtÞt
ffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
p dt
" #
ð2:26Þ
*(x,z)
z
x
–10 –8 –6 –4 –2 0 2 4 6 8 10
0
2
1
1.2
1.4
0.8
0.6
1.6
1
0.2
0.6
0.4
1.8
0.81.2
1.41.6
0.40.2
FIGURE 2.6 Reduced potential distribution c(x, z) = 2ereokc(x, z)/(s1 + s2) around a sur-
face with a sigmoidal gradient in surface charge density as a function of kx and kz calculatedfrom Eq. (2.25) for b/k¼ 1 at s2/s1¼ 3. From Ref. 5.
THE POISSON–BOLTZMANN EQUATION FOR A SURFACE 53
which is independent of b/k. Note that even in the limit of b/k¼1,
which corresponds to a sharp boundary between two regions of s1 ands2 (Eq. (2.23)), the potential varies sigmoidally in the x-direction unlike
s(x). This will be seen later again in Fig. 2.7, which shows the surface
potential c(x, 0).(b) In the opposite limit b=k � 1 (the charge gradient becomes small),
Eq. (2.25) becomes
cðx; zÞ ¼ s1 þ s22ereok
expð�kzÞ ð2:27Þ
Equation (2.27), which is independent of b/k and x, coincides with the
potential distribution produced by a plate with a uniform charge density
(s1 + s2)/2 (the mean value of s1 and s2), as expected.(c) When kz � 1, Eq. (2.25) becomes
cðx; zÞ ¼ s1 þ s22ereok
expð�kzÞ þ s2 � s1s1 þ s2
� �tanh
bx2
� �expð�kzÞ
� �
¼ sðxÞereok
ð2:28Þ
That is, the potential c(x, z) becomes directly proportional to the surface
charge density s(x) in the region far from the plate surface, as in the
case of uniform charge distribution (s¼ constant). The x-dependence ofc(x, z) thus becomes identical to that of s(x). It must be emphasized
here that this is the case only for kz � 1 and in general c(x, z) is notproportional to s(x).
(d) As kx!�1 or kx! +1, Eq. (2.25) tends to
cðx; zÞ ¼ s1ereok
expð�kzÞ as x ! �1 ð2:29Þ
cðx; zÞ ¼ s2ereok
expð�kzÞ as x ! þ1 ð2:30Þ
The potential distribution given by Eq. (2.29) (or Eq. (2.30)) agrees with
that produced by a plate with surface charge density s1 (or s2), asexpected.
The surface potential of the plate, c(x, 0), is given by
cðx; 0Þ ¼ s1 þ s22ereok
1þ 2kðs2 � s1Þbðs1 þ s2Þ
Z 1
0
sinðkxtÞffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
psinhðpkt=bÞ dt
" #ð2:31Þ
54 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
Figure 2.7 shows the distribution of the surface potential c(x, 0) alongthe plate surface as a function of kx for several values of b/k at
s2/s1¼ 3. Each curve for c(x, 0) in Fig. 2.7 corresponds to a curve for
s(x) with the same value of b/k in Fig. 2.5. It is interesting to note that
even for the limiting case of b/k¼1, which corresponds to a sharp
boundary between two regions of s1 and s2, the potential does not
show a step function type distribution but varies sigmoidally unlike
s(x) in this limit.
We now derive expressions for the components of the electric field E (Ex, 0, Ez),
which are obtained by differentiating c(x, z) with respect to x or z, as potential gra-dient (i.e., electric field) is formed along the plate surface.
Ex ¼ � @c@x
¼ � s2 � s1ereob
kZ 1
0
t expð�kzffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
p ÞcosðkxtÞffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
psinhðpkt=bÞ dt ð2:32Þ
and
Ez ¼ � @c@z
¼ s1 þ s22ereo
expð�kzÞ þ 2kðs2 � s1Þbðs1 þ s2Þ
Z 1
0
expð�kzffiffiffiffiffiffiffiffiffiffiffiffit2 þ 1
p ÞsinðkxtÞsinhðpkt=bÞ dt
" #
ð2:33Þ
FIGURE 2.7 Distribution of the reduced surface potential c*(x, 0), defined by c�(x, 0) =2ereokc(x, 0)/(s1 +s2), along a surface with a sigmoidal gradient in surface charge density as
a function of kx for several values of b/k at s2/s1 = 3. From Ref. 5.
THE POISSON–BOLTZMANN EQUATION FOR A SURFACE 55
2.3 DISCRETE CHARGE EFFECT
In some biological surfaces, especially the low charge density case, the discrete na-
ture of the surface charge may become important. Here we treat a planar plate surface
carrying discrete charges immersed in an electrolyte solution of relative permittivity
er and Debye–Huckel parameter k. We take x- and y-axes parallel to the plate surfaceand the z-axis perpendicular to the plate surface with its origin at the plate surface so
that the region z> 0 corresponds to the solution phase (Fig. 2.8). We treat the case in
which the surface charge density s is a function of x and y, that is, s¼ s(x, y).The electric potential c is thus a function of x, y, and z. We assume that the potential
c(x, y, z) satisfies the following three-dimensional linearized Poison–Boltzmann
equation:
@2
@x2þ @2
@y2þ @2
@z2
� �cðx; y; zÞ ¼ k2cðx; y; zÞ ð2:34Þ
which is an extension of the two-dimensional linearized Poisson–Boltzmann equation
(2.1) to the three-dimensional case. Equation (2.34) is subject to the following bound-
ary conditions at the plate surface and far from the surface:
@cðx; y; zÞ@z
����z¼0
¼ � sðx; yÞereo
ð2:35Þ
and
cðx; y; zÞ ! 0;@cðx; y; zÞ
@z
����z¼0
! 0 as z ! 1 ð2:36Þ
In Eq. (2.35) we have assumed that the electric filed within the plate can be neglected.
x
y
z
+
+
+
+
+
+
+ +
+
++
+
++
++
O
FIGURE 2.8 Plate surface carrying discrete charges in an electrolyte solution.
56 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
To solve Eq. (2.34), we write c(x, y, z) and s(x, y) by their Fourier transforms,
cðrÞ ¼ 1
ð2pÞ2Z
cðk; zÞexpðik � sÞdk ð2:37Þ
sðsÞ ¼ 1
ð2pÞ2Z
sðkÞexpðik � sÞdk ð2:38Þ
with
r ¼ ðx; y; zÞ; s ¼ ðx; yÞ; and k ¼ ðkx; kyÞ ð2:39Þ
where cðk; zÞ and sðkÞ are the Fourier coefficients. We thus obtain
cðk; zÞ ¼Z
cðrÞexpð�ik � sÞds ð2:40Þ
sðkÞ ¼Z
sðsÞexpð�ik � sÞds ð2:41Þ
Substituting Eq. (2.40) into Eq. (2.34), we have
@2cðk; zÞ@z2
¼ ðk2 þ k2Þcðk; zÞ ð2:42Þ
where
k ¼ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2x þ k2y
qð2:43Þ
Equation (2.42) is solved to give
cðk; zÞ ¼ AðkÞexpð�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞ ð2:44Þ
The unknown coefficient A(k) can be determined to satisfy the boundary condition
(Eq. (2.35)) to give
AðkÞ ¼ sðkÞereo
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p ð2:45Þ
We thus obtain from Eq. (2.37)
cðrÞ ¼ 1
ð2pÞ2ereo
ZsðkÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p expðik � sÞexpð�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞdk ð2:46Þ
This is the general expression for the electric potential c(x, y, z) around a plate
surface carrying a discrete charge s(x, y).
DISCRETE CHARGE EFFECT 57
Consider several cases of charge distributions.
(i) Uniform smeared charge density Consider a plate with a uniform surface
charge density s
sðsÞ ¼ s ð2:47Þ
From Eq. (2.41), we have
sðkÞ ¼ sZ
expð�ik � sÞds
¼ ð2pÞ2sdðkÞð2:48Þ
where we have used the following relation:
dðkÞ ¼ 1
ð2pÞ2Z
expðik � sÞds ð2:49Þ
Substituting this result into Eq. (2.46), we have
cðrÞ ¼ sereo
ZdðkÞffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p expðik � sÞexpð�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞdk ð2:50Þ
Carrying out the integration, we obtain
cðrÞ ¼ sereok
e�kz ð2:51Þ
which agrees with Eq. (1.25) combined with Eq. (1.26), as expected.
(ii) A point charge Consider a plate carrying only one point charge q situated at(x, y)¼ (0, 0) (Fig. 2.9).
sðsÞ ¼ qdðsÞ ð2:52Þ
From Eq. (2.41), we have
sðkÞ ¼ q
ZdðsÞexpð�ik � sÞds ¼ q ð2:53Þ
Substituting Eq. (2.53) into Eq. (2.46), we have
cðrÞ ¼ q
ð2pÞ2ereo
Z1ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
k2 þ k2p expðik � sÞexpð�
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞdk ð2:54Þ
58 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
We rewrite Eq. (2.54) by putting k�s¼ ks cos �:
cðrÞ ¼ q
ð2pÞ2ereo
Z 2p
k¼0
Z 1
k¼0
1ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p expðiks cos ��ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞk dk d�
ð2:55Þ
With the help of the following relation:Z 2p
0
expðiks cos �Þd� ¼ 2pJ0ðksÞ ð2:56Þ
where J0(z) is the zeroth-order Bessel function of the first kind, we can inte-
grate Eq. (2.55) to obtain
cðrÞ ¼ q
2pereo
Z 1
k¼0
1ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
p expð�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞJ0ðksÞk dk
¼ q
2pereo
1ffiffiffiffiffiffiffiffiffiffiffiffiffiffis2 þ z2
p expð�kffiffiffiffiffiffiffiffiffiffiffiffiffiffis2 þ z2
pÞ
ð2:57Þ
which is rewritten as
cðrÞ ¼ q
2pereore�kr ð2:58Þ
Note that Eq. (2.58) is twice the Coulomb potential c(r)¼ qe�kr/4preorproduced by a point charge q at distances r from the charge in an electro-
lyte solution of relative permittivity er and Debye–Huckel parameter k.This is because we have assumed that there is no electric field within the
plate x< 0.
x
y
z
O
FIGURE 2.9 A point charge q on a plate surface.
DISCRETE CHARGE EFFECT 59
(iii) Squared lattice of point charges Consider a squared lattice of point charges
q with spacing a (Fig. 2.10). The surface charge density r(x, y) in this case
is expressed as
sðsÞ ¼ qXm;n
dðs� mai� najÞ ð2:59Þ
where i and j are unit vectors in the x and y directions, respectively, and mand n are integers. From Eq. (2.41), we have
sðkÞ ¼ qPm;n
Zdðs� mai� najÞexpð�ik � sÞds
¼ qPm;n
exp½�ik � ðmaiþ najÞ�ð2:60Þ
Substituting this result into Eq. (2.46), we have
cðrÞ ¼ 1
ð2pÞ2q
ereo
Xm;n
Zexp½ik � ðs� mai� najÞ�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
k2 þ k2p expð�
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffik2 þ k2
pzÞdk
ð2:61Þ
Carrying out the integration, we obtain
cðx; y; zÞ ¼ q
2pereo
exp½�kffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiðx� maÞ2 þ ðx� naÞ2 þ z2
q�ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðx� maÞ2 þ ðx� naÞ2 þ z2q ð2:62Þ
which agrees with the results obtained by Nelson and McQuarrie [6].
0x
y
i
js
(m, n) = (2, 2)
(0, 1)
(2, 0)
(2, 1)
(0, 2)
(0, 0)
(1, 1)
(1, 0)
(2, 1)q
q
qqq
q q
a 2a
2a
a
FIGURE 2.10 A squared lattice of point charges q with spacing a on a plate surface.
60 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE
Figure 2.11 shows the potential distribution c near a plate surface carry-
ing a squared lattice of point charges q¼ e¼ 1.6� 10�19 C with spacing a¼ 2.5 nm in an aqueous 1-1 electrolyte solution of concentration 0.1M at
25C (er¼ 78.55) calculated via Eq. (2.62) at distances z¼ 0.5 nm and z¼ 1
nm. Figure 2.12 shows the potential distribution c(x, y, z) as a function of
FIGURE 2.11 Potential distribution c near a plate surface carrying a squared lattice of
point charges q= e= 1.6� 10�19 C with spacing a = 2.5 nm in an aqueous 1-1 electrolyte so-
lution of concentration 0.1M at 25C (er = 78.55) calculated via Eq. (2.62) at distances
z = 0.5 nm and z= 1 nm.
FIGURE 2.12 Potential distribution c(x, y, z) near a plate surface carrying a squared lat-
tice of point charges q= e = 1.6� 10�19 C with spacing a = 2.5 nm in an aqueous 1-1 electro-
lyte solution of concentration 0.1M at 25C (er = 78.55) as a function of the distance z fromthe plate surface at x = y= 0 and at x= y = a/2 = 1.25 nm, in comparison with the result for the
smeared charge model (dashed line).
DISCRETE CHARGE EFFECT 61
the distance z from the plate surface at x¼ y¼ 0 and at x¼ y¼a/2¼ 1.25 nm, in comparison with the result for the smeared charge model.
We see that for distances away from the plate surface greater than the
Debye length 1/k (1 nm in this case), the electric potential due to a lattice of
point charges is essentially the same as that for the smeared charge model.
For small distances less than 1/k, however, the potential due to the array of
point charges differs significantly from that for the smeared charge model.
REFERENCES
1. B. V. Derjaguin and L. Landau, Acta Physicochim. 14 (1941) 633.
2. E. J. W. Verwey and J. Th. G. Overbeek, Theory of the Stability of Lyophobic Colloids,Elsevier, Amsterdam, 1948.
3. H. Ohshima and K. Furusawa (Eds.), Electrical Phenomena at Interfaces: Fundamentals,Measurements, and Applications, 2nd edition, revised and expanded, Dekker, New York,
1998.
4. H. Ohshima, Theory of Colloid and Interfacial Electric Phenomena, Elsevier/Academic
Press, Amsterdam, 2006.
5. H. Ohshima, Colloids Surf. B: Biointerfaces 15 (1999) 31.
6. A. P. Nelson and D. A. McQuarrie, J. Theor. Biol. 55 (1975) 13.
62 POTENTIAL DISTRIBUTION AROUND A NONUNIFORMLY CHARGED SURFACE