The Electrostatic Repulsion between Charged Spheres from Exact

Solutions to the Linearized Poisson-Boltzmann Equation

A. B. GLENDINNING 1 AND W. B. RUSSEL

Department of Chemical Engineering, Princeton University, Princeton, New Jersey 08544
Received June 25, 1982; accepted August 27, 1982

An exact solution to the linearized Poisson-Boltzmann equation for the electrostatic potential
around two equal, charged spheres is constructed via a multipole expansion. Results for the repulsive
forces acting on the spheres are presented for 0.1 ~< aK ~ 20 over the full range of separations.
Comparison with the linear superposition and Derjaguin approximations defines their ranges of va-
lidity and highlights the failure of the latter at small separations for the case of fixed surface charge
densities.

INTRODUCTION surface potentials, or charges, over a broad

In aqueous colloidal dispersions electro-
static interactions play a major role in de-
termining the stability of the dispersion and
the magnitudes of various transport proper-
ties. Unfortunately, exact results for the re-
pulsive force, even for the case of two equal
spheres, are available only from computa-
tions at a limited number of conditions (1,
2) and asymptotic results for weak interac-
tions or thin double layers. The linear su-
perposition approximation (3) is valid in the
far-field limit, i.e., for separations of several
double layer thicknesses, while the Derjaguin
approximation (4) is exact when both the
Debye length and the separation are small
relative to the sphere radius. Both approaches
can accommodate the nonlinear Poisson-
Boltzmann equation. The regime of inter-
mediate double layer thicknesses with arbi-
trary separations and surface potentials re-
mains despite attempts (5) to patch together
the Derjaguin approximation, as an inner
solution, with the far-field superposition ap-
proximation.
Here we address the interaction between
range of separations and Debye lengths. An
exact solution to the linearized Poisson-
Boltzmann equation is constructed in terms
of multipole expansions centered on the two
spheres and the boundary conditions are ap-
plied through use of an addition theorem for
Bessel functions. Solutions for the interpar-
ticle force are presented for approach at con-
stant surface potential and at constant charge
density.
MULTIPOLE EXPANSIONS
For equilibrium double layers with small
surface potentials the electrostatic potential
4/is determined by
V2~ = (aK)Z~p [ 1]
with the potential scaled with 60 and lengths
with the radius; K-1 is the Debye length. In
spherical coordinates with axial symmetry
[1] has the general solution for 6 ~ 0 as
r ----* oO
~p(r, O) = ~ a,K,(aKr)Pn(cos O) [2]
n=0

equal spheres of radius a with small, equal with Kn the modified spherical Bessel func-
Present address: Raychem Corporation, Menlo Park, tion of the second kind and Pn the Legendre
California. polynomial.

95
0021-9797/83 $3.00
Copyright © 1983 by Academic Press, lnc,
Journal of Colloid and Interface Science, Vol. 93, No. 1, May 1983 All rights of reproduction in any form reserved.
 96 GLENDINNING AND RUSSEL

For two equal spheres the appropriate so- for Bessel functions (6) as described by Mar-
lution to [2] consists of two infinite sums of celja et al. (7) so that
the form shown, one based on the (rl, 01)
oo
coordinate system and the other on (r2, 02)
as defined in Fig. 1. The coefficients are equal
~b = ~ a~[Kn(axrOPn(cOs 01)
n=O
due to the symmetry of the problem. To ap-
ply the boundary condition at the surface of + X (2m + 1)B,mlm(arrOPm(cOs 01)], [3]
either sphere we transform one of the mul- m=O
tipole expansions into the other set of spher-
ical coordinates through an addition theorem where

c~3

Brim = ~ AnmKn+m-z~(arR)
v=0

1
+m-v)l(n+rn-2v+ 1)
Anm =
~rr(m+n-v+~)(n-v)!(m-v)lv!
Im is the modified spherical Bessel function 1, j =0
0fthe first kind, r the Gamma function, and ej= O, j>0 [4]
R the center-to-center separation. Note that
the expression for A~n in (7) has several ty- and ~ is the unit tensor. Except at touching
pographical errors. where the multipole expansion fails to con-
(a) Constant surface potential. For a fixed verge, the aj can be determined by truncating
surface potential 6o on both spheres the di- the infinite system and then inverting nu-
mensionless potential satisfies merically as discussed later.
~b= 1 on r l = 1. (b) Constant charge density. For fixed
charge densities ¢ on each sphere, setting
With [3] this determines the linear system of 6o = a¢l~ with ~ the dielectric permittivity
equations provides the boundary condition
(L + 6).A = e,
where
06
--1 on rl-- 1.
Or1
Aj = ajKj(aK)
The resulting linear system of equations has
Ljn = (2j + l)Bnslj(aK)/Ko(aK) the same form but with

7-
0
3_
FIG. 1. C o o r d i n a t e s y s t e m for t w o - s p h e r e interactions.

Journal of Colloid and Interface Science, VoL 93, No, 1, May 1983
 POISSON-BOLTZMANN EQUATION 97

Aj = --(aK)ajK~(aK) with the argument of all the Bessel functions

being aK and
Lj, = (2j + 1)B,,jI'j(a~c)/K'(aK). [5]
The prime on the Bessel functions indicates CI (n, m)
differentiation with respect to the argument.
2(m + 1)
(2m+3)(2m+ 1)' n = m + 1
FORCE CALCULATION
2m
Both the pressure and the Maxwell stresses [lO]
contribute to the force (3) as ( 2 m + l ) ( 2 m - 1)' n = m - 1

_ + 1 .E2)n-(E.n)E] dA. 0, n#m+ 1.

[61 For constant surface charge

The electric field E is scaled with ~o/a and
the force with ~b2. n is the unit normal on + (,- .)4°ffL
sphere 1 and \ OM _1

1 22 +2(1-Fz 2)~ du
H = ~(aK) ¢ [7]
oo

is the local excess osmotic pressure due to = 7r ~ an[(a~c)2Kn ~ aiKiCl(n, i)

ions in the double layer. The sole nonzero n=0 i=0

component of the force, of course, acts along oo co

the line of centers with magnitude + 2(aK)ZKn Z ai E (2j + 1)BijljCl(rt, j)
i=0 j =0
F = ~ {[(a~)2¢ ~ + E0~ - E l ] .
oo oo
I
+ (aK)2 ~, (2m + 1) BnmIm ~,
+ 2ERE0(1 - u2) 1/2} & , [81 m=0 i=0

with t~ = cos 0t.

For constant potential [8] reduces to × ai ~ (2j + 1)BqI~G(m, j)
j=0

F = -~r
f_ 1
E~ u d .
of)

+ K. ~ aiKiC3(n, i) + 21£.
i=0
o(3

i=0
oo oo
co
= (a~) 2 ~, a, [K',~ ~ aiK}Cffi, n)
n=0 i=0 × ai ~ (2j + 1)BijIj C3(n, j)
j=0
oo co
o~ o:3 o~
+ 2K" ~ ai ~ (2j + 1)BqI~Cl(j, n)
i=0 j =0 + ~ (2m + l)B.mlm ~ ai ~ (2j + 1)
m=0 i=0 j =0

+ Z B.m(2rn + 11I" 871"

m=0 i=0 × BqljC3(m, j) + 8B.111] + ~ - alKl ,
c:(3
[11]
× ai ~ (2j + 1)BJ~C,(m, j)] [9]
j=0 where

Journal o f Colloid and Interface Science, Vol. 93, No. 1, May 1983
98 G L E N D I N N I N G A N D RUSSEL

TABLE I next section to reconsider the limit of thin

N u m b e r of Terms for Four-Place Convergence
double layers.

C O R R E C T I O N TO THE D E R J A G U I N
Constant potential Constantcharge APPROXIMATION

ar (r-2) l 2 lO 20 1 2 10 20 The Derjaguin approximation for the elec-

trostatic force between charged spheres with
0.1-0.5 11 13 21 25 16 22 42 44
thin double layers has been widely exploited
0.5-1.0 8 9 14 22 8 10 27 38
1.0-2.0 6 9 14 17 7 10 17 27
but only recently (2, 8) tested to determine
2.0-3.0 6 7 14 17 6 7 15 21 the range of aK for which it is numerically
3.0-4.0 5 7 13 16 5 6 12 18 accurate. In this section we derive the next
4.0-5.0 5 6 12 15 3 5 12 16 term in a regular perturbation expansion for
>5.0 4 4 9 15 3 4 11 11 ar >> 1 to gauge the error and to provide a
check for our numerical results. This extends
the work of Ohshima et al. (8) to include the
C3(n, m) case of constant surface charge.
Expressing [1] in cylindrical coordinates
2(m + 1)(m + 2)m centered at the midpoint between the spheres

I
(2m+3)(2m+ 1)' n=m+ 1 with the rescaling
2 m ( m + 1 ) ( r n - 1) Z ~ z/aK
= (2m + l)(2m 1) ' n m- 1
r ~ r/(aK) 1/2
O, n4=m++_l. produces
024 1 1 0 04
The numerical evaluation of the forces in- F-- [12]
volved first truncating the linear systems [4] Oz ~ ~b aK r Or Or
and [5] and using Gaussian elimination to with
determine the coefficients a~ and then sum- 04 0 at z 0
ming [9] or [11]. Double precision was used Oz
routinely with a few computations in quad- and either
ruple precision to establish that round-off 4=1
error was insignificant. The m a x i m u m num- or
ber representable on the computer ( 10 75) lim- a~ nr a~
nz-- + - 1
ited the computations to aK < 35. Recursion Oz aK Or
formulas determine the Kn accurately and
on the sphere surface defined by
rapidly from K0 and K1 but the rapid growth
of round-off error dictated that the exact se-
ries representation be used for In. + r7.
For aK ~ O(1) 10 terms in the expansion
suffice for all but the smallest separations. where 2ho is the m i n i m u m separation and
For dimensionless separations less than 0.1 the scaled normals are
up to 44 terms were required to converge the nz = - ( 1 + rZ]-l/ZaKj
force to within 0.1% (Table I).
The results are most meaningful when
compared with the limiting cases noted in [ r4 1,2
= r-1 -
the introduction. Hence we digress in the nr t (LTl "

Journal of Colloid and Interface Science, Vol. 93, No. 1, May 1983
 POISSON-BOLTZMANN EQUATION 99

For ag >> 1 we expand as

0 [1~] 02@2 @2-- 10 0@1
-~K Oz 2 r Or r O~
@ = @1 + @2+ . . .
aK 0@2
-0 at z=0
Oz
lr2 _lr 4
h(r) = ho + ~ + 8 aK + " ' " 0@1
@2 = - & - - [16]
Oz
or
=hi+h2+ - - , . ,

aK 0% (hi - ho){~z' + 2 0@1

r2 1 02@1~
n~=-I +2aK + "'" -- ~ (hi - ho) ~ - ~ at z = hi.

nr=r+ ..- [13] The solutions are:

(a) constant potential
and collapse the second b o u n d a r y conditions cosh z
onto z = hi through the Taylor series @1 -- - -
cosh hi

@(h) = @1(hl) sinh z

@2 = f z - -
cosh hi
1{ 0@1 }
+ - - @2(hl)+h2
aK &-z
(hi) + - • •
- [
@1 tanh hi f h l + ~ (hi - ho) 2 , 1 1 [17]

0@ 0@1 1 10@2 with

O~ (h) = O z (hi) + --aK ( Oz (hi) f = tanh h i + ( h i - ho)(1 - 2 tanh2h0;
(b) constant charge
+ (hi -~ h°)2 02@10z
2 (hi)} + • • ". [141
cosh z
@1 sinh hi
Then the potential is determined by sinh z
@2 = z sinh h~ {ctanh hi + (hi - ho)
02@1
O(1) Oz 2 @1 = 0 sinh z
× (1 - 2 ctanh 2 hi)}
sinh hi
0@1 - 0 at z=0 × ctanh hi{ 1 + h i ctanh hi
Oz

@1 = 1 2 hi(hi - ho) 1 (h~ - ho2)} [18]

sinh 2 hi 2
0@1 In both cases the correction for finite aK re-
or - 1 at z=h~, [15]
Oz duces the potential in the gap between the
particles, e.g.,

..... (ho2 tanh 2 ho, const potential

¢2( 0 , O)
-~l(O'O)~,ctanh" ho(1 + ho tanh ho), const charge

<0. [19]

Journal of Colloid and Interface Science, Vol.93, No. 1, May 1983

100 GLENDINNING A N D RUSSEL

3°L
2£ I

2.2

uY

1.4

1.0
0 .6 12 1,8 2.4 3D
oK ( r - 2 )

FIG. 2. Ratio of linear superposition force to exact force for constant potential. (-- • --) aK = 0.1,
(. . . . ) aK = 0 . 5 , ( ) aK = 1.0, ( .... ) aK = 10.0.

The force acting on either particle [6] can with the upper sign pertaining to constant
be converted through use of the divergence potential and the lower to constant charge.
theorem to an integral over the symmetry Here
plane of the form e-2h0
Fo = 2~-aK 1 _ e -2h°
F=Trfo~I(O~b~2+aKlp2}
is the Derjaguin result. Note that the limiting
forms
= aK +- 1~2
0 aK I 0.102,
0:(F ) const potential
+ (h,- ho,t l j; dh,. [2o] h o ~ F-d- 1 a K ~ , -1/ho,
const charge
The correction term consists of a negative
1
effect of the reduced potential within the gap, h0~: -I aK~+--h0 [221
which lowers the local osmotic pressure, and -2
a positive contribution from the Maxwell
stress arising from the O(aK) -1/2 radial gra- indicate that the Derjaguin approximation
errs seriously in the case of constant charge
dients in ~,. Hence the correction can be of
at small separations. And in that limit the
either sign.
entire expansion breaks down when ho
The final result for the force is
< (aK)-l since the correction becomes com-
(aK)_i parable to the leading order term. The results
F=Fa 1 1 + e -2h° for constant potential conform with those of
Ohshima et al. (8).
1 e_4h °

× T- 1 + h o l__+_e-2h° DISCUSSION OF RESULTS

-t- 6e2ho(1 ± e-2ho)2 ln(1 + e 2ho)l} [21] The linear superposition approximation
for the force has the dimensionless form (3)

Journal of Colloid and Interface Science, Vol. 93, No. 1, May 1983
 PO1SSON-BOLTZMANN EQUATION 10t

6,ol

o.of'!/ ', \

L.L~
Cu~O

20 \\')',
o .6 t2 1.8 2.4 30
ex(r-2)

FIG. 3. R a t i o o f linear superposition force to exact force for c o n s t a n t charge. ( - - . - - ) aK = 0.1,

) aK 1.0, ( - - - - - ) aK = 2.0, ( . . . . . ) aK = 5.0, ( . . . . ) aK = 10.0.

(1 + aKR) result at small separations. The approxima-

F- R2 tion becomes exact except at contact for
aK ~ 0 but the error increases with increasing
const potential ar at all separations. The force ratio is in-
J
x exp{--aK(R I

2)} verted between the two figures since linear

1 (1 + aK) 2,
~ const charge
[231
with the difference between the two cases
arising solely from the scaling of the force.
The curves in Figs. 2 and 3 illustrate the de-
viation of this far-field limit from the exact
superposition overestimates the force for in-
teractions at constant potential but under-
estimates the effect at fixed surface charge
density.
Figure 4 compares the exact theory with
the Derjaguin approximation for the con-
stant potential case. For aK > 1 the agreement

3.0

2.4

1.8

u_
~ t,2

r I I I
0 1.0 2.0 3.0 4.0 5.0
Gx(r-2)

FIG. 4. R a t i o o f D e r j a g u i n force to exact force for c o n s t a n t potential. ( ) a~ = 1.0, ( - - - - - ) aK

= 2.0, ( . . . . ) aK = 10.0, ( - - - ) aK = 20.0.

Journal of Colloid and Interface Science, Vol. 93, No. 1, May 1983
102 GLENDINNING AND RUSSEL

-I

-2 I I I I
0 I 2 3 4
az (r-2)
FIG. 5. C o r r e c t i o n t o D e r j a g u i n f o r c e f o r c o n s t a n t p o t e n t i a l . ( ) aK = 1.0, ( - - - - - ) aK = 2 . 0 ,
(.... ) a~ = 10.0, ( . . . . . ) aK = 2 0 . 0 , a n d ( ) Eq. [36].

is quite good. The disparity increases with The situation for approach at constant
separation but only becomes significant for charge shown in Fig. 6 is quite different. The
aK ~ O(1) since the forces decay exponen- Derjaguin approximation becomes accurate
tially. The plot of the correction to the Der- for O(1) separations only for aK > 30 and
jaguin result scaled by aK in Fig. 5 conforms always errs substantially at small separations.
to the trends predicted by the O(1/aK) per- Figure 7 confirms this error to be in quali-
turbation theory in the previous section. For tative accord with the O(1/aK) correction
aK > 20 the first-order perturbation theory derived in the previous section, with quan-
becomes exact. titative agreement indicated for aK > 20. The

.J
.J
.J
~J
.J

II•Zz•-z_--
O/
0
~
I
----~
~

2
I
3
I
4
aK(r-2)
I
5
I
6
----

I
7 8
I

FIG. 6. R a t i o o f D e r j a g u i n f o r c e t o e x a c t f o r c e f o r c o n s t a n t c h a r g e . ( - - ) aK = 1.0, ( - - - - - ) aK = 2 . 0 ,
(.... ) aK = 10.0, ( - - - ) aK = 2 0 . 0 .

Journal of Colloid and Interface Science, Vol. 93, No. 1, May 1983
 . ~.'i ....... -_ . . . . . . . . - ..... 7 ..........
i

I I I I I
0 I 2 3 4
oK{r-2)

FIG. 7. C o r r e c t i o n to D e r j a g u i n force for c o n s t a n t charge. ) aK 1.0, (-----) aK = 2.0,

(. . . . ) aK = 10.0, ( - - - ) au = 20,0, a n d ( ) Eq. [36].

10 /!
iI
//
//
iI
ii
iI
6 /
/
i/
oK

LSA

0 ~ 2 ~ 4
ox(r -2)

iO

E
4

LSA
2

0
o ', 4
aK (r-2)

FIG. 8. V a l i d i t y o f results for (A) c o n s t a n t p o t e n t i a l a n d (B) c o n s t a n t charge. W i t h i n each region, the

label d e n o t e s which, if any, a p p r o x i m a t e f o r m for the force is w i t h i n 10% o f the e x a c t value.

103

Journal of Colloid and Interface Science, Vol. 93, No. I, May 1983
104
problem at small separations arises from the
increasing magnitude of radial gradients in
potential, i.e., the term on the fight-hand side
of [12]. As that term becomes large the Der-
jaguin approximation, and the regular per-
turbation expansion of the previous section,
breaks down. At the same time, however~ the
potential becomes sufficiently large to render
invalid the linearization on which the entire
analysis is based.
Figures 8A and B summarize the regions
of applicability for the various theories for
constant potential and constant charge, re-
spectively. The boundaries correspond to ap-
proximately a 10% error for the approximate
theories. At constant potential the approxi-
mations cover much of the domain, but not
at constant charge since the Derjaguin result
only becomes accurate for aK > 30.
Available numerical solutions (2) define
in part the effect of nonlinearity on the con-
clusions presented here. For constant poten-
Journal of Colloidand InterfaceScience, VoL93, No. 1, May 1983
GLENDINNING AND RUSSEL
tial conditions the error in the force is ~ 10%
at e~ko/kTS4 for aK = 10, but the criteria for
validity of the aK >> 1 approximation appear
to be unaffected. The situation for the con-
stant charge case, where the error could be
much greater, remains to be defined.
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1. McCartney, L, N., and Levine, S., J. Colloid Inter-
face Sci. 30, 345 (1969).
2. Chan, B. K. C., and Chan, D. Y. C., preprint.
3. Bell, G. M., Levine, S., and McCartney, L. N., J.
Colloid Interface Sci. 33, 335 (1970).
4. Hogg, R., Healy, T. W., and Fuerstenau, D. W.,
Trans. Faraday Soc. 62, 1638 (1966).
5. Bell, G. M., and Peterson, G. C., J. Colloidlnterface
Sci. 41, 542 (1972).
6. Langbein, D., "Theory of van der Waals Attrac-
tion." Springer, Berlin, 1974.
7. Marcelja, S., Mitchell, D. J., Ninham, B. W., and
Sculey, M. J. J. Chem. Soc. Faraday Trans. H
73, 630 (1977).
8. Ohshima, H., Chan, D. Y. C., Healy, T. W., and
White, L. R., J. Colloid Interface Sci. 90, 17
(1982).