Approximate Expressions for Retarded van der Waals Interaction

JOHN GREGORY
Deportment o f Civil Engineering, University College London, Gower Street,
London WC1E 6BT, United Kingdom
Received September 29, 1980; accepted February 16, 1981

Several approximations for retarded van der Waals interaction between plates, between spheres,
and for the sphere-plate system are considered. For the interaction of fiat plates, a single ex-
pression is shown to be an adequate substitute for two empirical formulae of Overbeek. This ex-
pression is then used to derive a simple result for retarded interaction between unequal spheres
at close approach which agrees fairly well with "exact" computations up to separations of about
10% of the sphere radius. An equivalent expression applies to the sphere-plate system but in this
case an even simpler result is shown to give reasonable agreement with exact computations up to
distances of about 20% of the sphere radius. These approximations take the form of simple unre-
tarded Hamaker formulae, together with a correction factor which depends on the separation
distance and the characteristic wavelength of the dispersion interaction. They should find application
in problems of colloid stability and particle deposition.

INTRODUCTION tions greater than a few nanometers.

In studies of colloid stability or particle
deposition on surfaces it is often necessary
to calculate the van der Waals attraction be-
tween approaching particles as a function of
separation distance. There are, essentially,
two approaches to such computations. In
the first, due largely to Hamaker (1), the
interaction between macroscopic bodies is
derived by a pairwise summation of all the
relevant intermolecular interactions. The
second, more rigorous, approach is based
on Lifshitz theory (2, 3) and depends en-
tirely on macroscopic electrodynamic prop-
erties of the interacting media. Despite a
number of shortcomings, the older, Hamaker,
approach continues to be quite widely used,
mainly because of its greater convenience
and the fact that, for many practical sys-
tems, the results are not far wrong.
Owing to the electromagnetic nature of
the interaction, there is a finite time of
propagation between bodies and this leads
to r e t a r d a t i o n and a reduced interaction.
This effect can become very important,
especially in particle deposition, at separa-
138
0021-9797/81/090138-08502.00/0
Copyright© 1981by AcademicPress,Inc.
All rightsof reproductionin any formreserved.
Although the full Lifshitz treatment im-
plicitly incorporates the retardation effect,
whereas the original Hamaker approach
does not, it is not difficult, in principle, to
modify the latter to account for retardation.
The usual approach is to carry out Hamaker-
type integrations for the appropriate geom-
etry (e.g., interacting plates or spheres),
using expressions for retarded intermolec-
ular attraction. However, there is a dif-
ficulty with this approach, which has not yet
been satisfactorily overcome.
This difficulty arises from the lack of a
convenient expression representing re-
tarded interaction between molecules over
the entire range of separation distances.
Overbeek (4) found that the Casimir-Polder
(5) results for retarded interaction could
be represented as an empirical correction
factor to the London dispersion energy, U,
between two molecules separated by a
distance R:
B
U - --f(p), [1]
Re
where B is the London coefficient for the
Journal of Colloidand InterfaceScience, Vol.83, No. 1, September1981
 VAN DER WAALS INTERACTION 139

interacting molecules and the correction
f a c t o r f ( p ) is a function of reduced distance,
p = 2"n'R/h, where h is the "characteristic
wavelength" of the interaction, often as-
sumed to be about 100 nm.
Unfortunately, Overbeek was unable to
find a single expression for f (p), but gave
the following two empirical formulae:
0<p<3:
f ( p ) = 1.10 - 0.14p,
3<p<~:
f(p) = 2.45//) - 2.04/p 2.
Schenkel and Kitchener (6) found an ex-
pression valid for p > 0.5, matching the
Overbeek results with an accuracy of better
than 15%:
0.5 < p < 2:
f(p) = 2.45//) - 2.17//) 2 + 0.59/p 3.
Equations [2]-[4] have been used to
derive a number of expressions for retarded
interaction in the plate-plate, s p h e r e -
sphere, and sphere-plate cases.
INTERACTION BETWEEN FLAT PLATES
where A is the Hamaker constant for the
interacting media.
For very small distances Eq. [5] reduces
to the unretarded Hamaker result for plates:
V = - A / 1 2 7 r x 2. [7]
The short-range expression, Eq. [5]
contains more terms than Eq. [6] since
both Eqs. [2] and [3] have to be used in the
[21 integration. For separations greater than
3h/2~-, all interacting molecules must be
separated by at least this distance, so that
[3] only Eq. [3] needs to be used.
Equations [5] and [6] have recently been
shown (8) to give excellent agreement with
direct measurements of retarded van der
Waals attraction.
Corresponding expressions for plates of
finite thickness have been given by Hunter
[4] (9) and Vincent (10).
It has been found that Eqs. [5] and [6]
can be reasonably well represented by a
single expression covering the entire range
of separation distances. The result can best
be expressed as a correction factor to the
unretarded Hamaker fiat-plate expression,

For semi-infinite flat plates separated

by a distance x, the integration is quite 1 + bx/h
straightforward and Overbeek (7) obtained
A
the following results for the interaction
energy, V, per unit area: - 1 2 r r x 2 f ' ( x ). [8]

x < 3X/2~-: The constant b can be chosen to give

exact agreement with the Overbeek ex-
V- A[0.0842~_/x
-7 0.093(Tr)x
pressions at any distance, but, for most
purposes, a value fitted at x = 3X/2~- should
be acceptable. At this distance, the required
0.58(~) "~ '~ ~
value is b = 5.32. The correction factor
f ' ( x ) obtained in this way is plotted in Fig.
+ 0.0026 (UI x2 , [5] 1, together with the corresponding factor
calculated from Eqs. [51 and [6] (each used
x > 3X/27r: over the appropriate region and the results
V - A [0.0408( X 1 plotted as a smooth curve). The agreement
is quite good over a wide range of separa-
~- L ~ \ ~ ) tions, the maximum error of about +20%
0.0086 ( h / 2 occurring at large distances. At close ap-
[6]
proach, Eq. [8] with b = 5.32 gives results
Journal of Colloid and Interface Science, Vol. 83, No. 1, September 1981
140
which are, at worst, about 10% lower than
the Overbeek value. A value of b can be
chosen to give still better agreement at close
approach of the plates but the discrepancy
at large separations then becomes greater.
INTERACTIONS INVOLVING SPHERES
For spheres, the Hamaker integration
procedure becomes considerably more
difficult, owing to the lack of a single
expression for retarded intermolecular at-
traction. One method is to use the Schenkel
and Kitchener expression, Eq. [4], even
though this is not valid at close approach.
Schenkel and Kitcbener (6) derived a result
for equal spheres and Ho and Higuchi
(11) obtained equivalent expressions for
unequal spheres and the sphere-plate case.
The results quoted are only appropriate for
separation distances much less than the
sphere radii (d ~ a). Coupled with the
d > M4~- condition (since p > 0.5) and
assuming k = 100 nm, this restriction
means that the results are not appropriate
for particles smaller than about 2 ~m
diameter and for separation distances less
than about 8 nm, which in many practical
cases is the region of most interest. The Ho
and Higuchi result for the energy of inter-
action between unequal spheres is:
d > k/4~-, d ~ a~:
Aa,a2 F2.45i k \
V~ = - 6(al +a2)d[-i-~!---£)
60~.2 ~- 280~.------T
where ai and a2 are the sphere radii (ai < a2)
and d is the separation distance.
When d ~ h retardation is insignificant
and the simple, unretarded, Hamaker ex-
pression may be used:
d ~ a~:
Vs
Aa~a~
6(al + a~)d
Journal of Colloid and Interface Science, Vol. 83, No. 1, September 1981
JOHN GREGORY
lo
'[ o.o
V(x)
04
o
×(nm)
ioo I~o
FIG. 1. The empirical retardation factor for plates
f'(x) from Eq. [8] with b = 5.32 and X = 100 nm
(dashed line) compared with the corresponding factor
calculated from the Overbeek expressions, Eqs.
[5] and [6] (full line).
The term in square brackets in Eq. [9]
is thus a correction factor to be applied to
the unretarded Hamaker expression.
By putting al = a2 in Eq. [9] the Schenkel
and Kitchener result for equal spheres is
recovered and, by letting a2 --~ ~, the corre-
sponding expression for sphere-plate inter-
action is obtained.
Schenkel and Kitchener (6) also found
an empirical expression valid for intermedi-
ate distances by interpolation between the
retarded and unretarded expressions, The
same correction factor was quoted by Ho
and Higuchi (11) for the case of unequal
spheres and the resulting expression, valid
for distances up to about k/~- is:
0 <d< k/~'id~al:
Aala2 ( 1 )
Vs- 6(al + a 2 ) d 1 + ll.12d/k [11]
It is worth pointing out that the correc-
, tion factor in Eq. [11] for retarded interac-
tion between spheres is of just the same form
as that found for flat-plate interaction in
Eq. [8].
Recently, Czarnecki (12) has carried out
complete Hamaker-type integration of Eq.
[4] for the sphere-plate case, so that the
d ~ a restriction is lifted. However, his
[10]
expression must still become very inac-
curate at separations less than about 8 nm.
 VAN DER WAALS
The result is:
d > M4~r:
[2.45h(d - a d+3a ) spheres over the important region of separa-
Vsp = A L6---~ \ (d + Ua)2
2.17X2 {d - 2a d+4a I the interaction energy between spheres at
7207r 2 ~ -~a-
0.59X 3 /d - 3a ' +5a ll
+ 50407r a
/ ~a- (d + 2-~4]J " (12)
Expressions for retarded interaction be-
tween spheres, based on the two Overbeek
expressions, Eqs. [2] and [3], have been
derived by Vincent (10) and Clayfield et al.
(13). Vincent carried out separate integra-
tions of Eqs. [2] and [3], for unequal
spheres, to obtain" short-range" and "long-
range" formulae, and assumed that the
"cross-over point," where the two expres-
sions gave the same result, represented the
limit of validity for each. This point was
determined graphically for several different
sphere sizes. This procedure is open to
doubt since, even for the short-range case,
the total interaction includes contributions
from regions of the spheres interacting
over considerably greater distances than
the distance of closest approach of the
sphere surfaces. Thus, Vincent's short-
range expression is unlikely to be reliable
except at very close approach of the
spheres. The long-range expression is only
valid at separation distances which are too
large to be of much interest for colloidal
particles.
Clayfield et al. (13) carried out lengthy
integrations for equal spheres and for the
sphere-plate case incorporating both Eqs.
[2] and [3], giving results which should
be valid at all separation distances. Within
the limitations of the Hamaker approach,
the Clayfield expressions can be regarded
as " e x a c t , " although they are extremely
cumbersome.
It would be useful to have a much simpler
Journal of Colloid and Interface Science, Vol. 83, No. 1, September 1981
INTERACTION 141
expression, suitable for, say, programmable
calculators, giving an adequate representa-
tion of the retarded interaction between
tion. Such an expression can be derived
by the Deryagin method (14), which enables
close approach to be derived from the
corresponding flat-plate expression. The
interaction energy between two spheres,
radii al and a2, separated by a distance
d is given by:
Vs- 2-zra--ja2 V(x)dx, [13]
(al + a2)
where V(x) is the interaction energy per unit
area between parallel flat plates separated
by a distance x.
Using Eq. [8] for the retarded plate inter-
action energy, the integration can be carried
out immediately to give:
d ~ al:
Aaaa2
gs -
6(al + a2)d
× 1- In 1 + -- . [14]
h bd
The term in square brackets is a correc-
tion factor to the unretarded Hamaker ex-
pression, Eq. [10] and tends to unity as
d/X ~ 0. The constant b could be chosen
to give the best fit with " e x a c t " computa-
tions, such as those of Clayfield et al. (13),
but, for the sake of comparison, the value
found appropriate for plate interaction (b
= 5.32) will be retained.
Equation [14] only applies to separations
much smaller than the particle radius. This
is a purely geometric restriction, imposed
by the use of the Deryagin integration
procedure, and has nothing to do with re-
tardation. The same restriction applies to
Eqs. [9] and [11] and is not a serious
limitation in practice, as will be shown
below.
142
RESULTS OF COMPUTATIONS
A. Interaction of Equal Spheres
I n Figs. 2 and 3, the r e t a r d e d interac-
tion e n e r g y b e t w e e n equal s p h e r e s given b y
the n e w a p p r o x i m a t i o n , Eq. [14] (with al
= az), is c o m p a r e d with values f r o m o t h e r
expressions:
(1) T h e full, u n r e t a r d e d , H a m a k e r ex-
pression:
A [ 2a_2 + 2a2
Vs -
6 [ d ( 4 a + d) (2a + d) z
d(4a + d) ]
+ In (SSa +-dS J " tlSl
(2) T h e a p p r o x i m a t e , u n r e t a r d e d , Ha-
m a k e r e x p r e s s i o n f o r v e r y close a p p r o a c h o f
the spheres, o b t a i n e d f r o m Eq. [10] with
o.1
i ~o
d (nrn)
FIG. 2. The effect of retardation on the interaction
of equal spheres, radius 1 /.~m. The reduced interac-
tion Vs/A is plotted against separation distance d. Cal-
culations based on: (1) The full, unretarded Hamaker
expression, Eq. [15]. (2) The approximate, unretarded
Hamaker expression, Eq. [16]. (3) The "exact" re-
tarded results of Clayfield et al. (13). (4) The "short-
range" retarded result of Vincent (10). (5) The Schen-
kel and Kitchener expression, Eq. [9], with al = a~.
(6) The interpolated result of Schenkel and Kitchener,
Eq. [11]. (7) The new approximation, Eq. [14]. The
"exact" expressions for unretarded and retarded inter-
action, curves (1) and (3), are plotted as full lines and
the approximate expressions as broken lines.
Journal of Colloid and Interface Science, Vol. 83, N o . 1, S e p t e m b e r 1981
JOHN GREGORY
\
\\
t~7
aOI
1o 1oo
d(nm)
Fia. 3. Same as for Fig. 2, but for spheres of 100
nm radius and omitting the results based on Eq. [9].
a I = a 2 ----a:
d~a:
V~ = -Aa/12d [16]
(3) T h e " e x a c t " r e t a r d e d results o f Clay-
field et al. (13).
(4) T h e " s h o r t - r a n g e " r e t a r d e d result o f
V i n c e n t (10) (his Eq. [10]).
(5) T h e e x p r e s s i o n o f S c h e n k e l and
K i t c h e n e r (Eq. [9] with at = a2), valid f o r
d > h/47r and d ~ a. (N.B. these results
are not i n c l u d e d in Fig. 3 since the ex-
p r e s s i o n is not valid f o r particles with
a = 100 nm.)
(6) T h e interpolated result o f S c h e n k e l
1oo
and K i t c h e n e r , Eq. [11], valid for 0 < d
< h/Tr and d ~ a.
T h e c o m p u t a t i o n s h a v e b e e n c a r d e d out
for particles o f t w o different sizes: a = 1
~ m and a -- 100 n m , with the c h a r a c t e r i s t i c
w a v e l e n g t h , h, a s s u m e d to be 100 nm. T h e
results are plotted as r e d u c e d interaction
e n e r g y , Vs/A, w h e r e A is the H a m a k e r
constant.
Several points e m e r g e f r o m t h e s e results,
s o m e o f t h e m already well k n o w n and re-
stated here:
(a) T h e c o m m o n l y u s e d s h o r t - r a n g e unre-
t a r d e d H a m a k e r e x p r e s s i o n , Eq. [16], is a
 VAN DER WAALS INTERACTION 143

rather poor approximation and begins to a), i.e., Eqs. [9], [11] and [14], it might
depart seriously from the full expression, be thought that departure from the exact re-
Eq. [15], at separations greater than a few sults would occur at about that distance
percent of the particle radius. When d where the simple Hamaker expression,
= a/lO, Eq. [16] gives results which are Eq. [16] begins to depart from the full,
about 70% too high. unretarded expression, Eq. [15]. Figures 2
(b) Retardation begins to be appreciable and 3 show, however, that the retarded
at very small separation distances, espe- expressions are considerably better in this
cially for larger particles. For a = 1/~m and respect and have a usefully extended range
d = 1 nm (only 1% of the characteristic of validity.
wavelength) retardation already reduces the
interaction energy by 11% and at 10 nm B. S p h e r e - P l a t e I n t e r a c t i o n
separation by about 50%.
(c) The short-range expression of Vin- The case of a sphere and an infinite flat
cent is quite good for the smaller particles, surface is of considerable interest in prob-
where it matches the Clayfield results up lems of deposition and filtration. Usually,
to about 10 nm separation reasonably the particles are so much smaller than the
well, but changes sign at d -~ 40 nm. For collector that the sphere-plate model is a
the larger particles Vincent's expression justifiable assumption.
is of much more limited range. In Figs. 4 and 5, the reduced sphere-
(d) The approximate expression of Schen- plate interaction energy, Vsp/A, is plotted as
kel and Kitchener, Eq. [9], clearly should a function of separation distance for two
not be used at small separations, where different sphere sizes, a = 1 /zm and 100
it gives results which are much too high. nm, as used previously. The computations
For the 1-/zm particles, a practical lower are based on the following expressions:
limit would be d = 5 nm. For smaller (1) The complete unretarded Hamaker
particles, this expression should not be used expression:
at all.
(e) The interpolated result of Schenkel Vsp -
A[a
+ - -
a
and Kitchener, Eq. [11], agrees well with 6 d d+2a
the Clayfield results for separations up to
about 5% of the particle radius. The de- + In d + 2a [17]
partures at greater separations appear to be
due primarily to the geometric restriction (2) The approximate, unretarded, Ha-
d ~ a, rather than to exceeding the stated maker expression, valid only for very close
upper limit of d -- h/Tr (about 30 nm). approach:
(f) The new approximation Eq. [14] gives d ~ a :
the best overall agreement with the Clay-
Vsp = - A a / 6 d . [18]
field results, although for 1-/zm spheres the
agreement is only marginally better than (3) The "exact" retarded results of Clay-
Eq. [11]. Again, the approximation begins field et al. (13).
to become inaccurate at separations greater (4) The expression of Czarnecki (12),
than about 5% of the particle radius, al- valid for distances greater than about 8
though for practical purposes Eq. [14] nm, Eq. [12].
should be acceptable up to d ~- a/lO. (5) A modified version of the Schenkel
(g) For those retarded expressions which and Kitchener interpolation formula Eq.
are restricted to small separations (d [11], in which the numerical constant in the

Journal of Colloid and Interface Science, Vol. 83, No. 1, September 1981
144
correction factor has been chosen to give an
exact fit with the Clayfield computations
at a separation distance of 10% of the
sphere radius, d = a/lO. For a = 1/xm and
a = 100 nm the required constants are 13.88
and 14.02, respectively. Since these are so
similar, a value of 14 has been used in both
cases, giving:
Vs, ( 1
Aa_6_d\1 + 14d/)t) "
(6) The previously derived approxima-
tion, Eq. [14] with a2 = o% and retaining
the value of b = 5.32.
The following comments concerning
these sphere-plate results can be made:
(a) The simple unretarded Hamaker ex-
pression, Eq. [18], is a slightly better
approximation than the corresponding ex-
pression for equal spheres, Eq. [16], but still
gives results about 35% higher than the full
expression at d = a/lO and becomes much
worse at larger separations.
(b) Retardation has about the same sig-
nificance as in the sphere-sphere case.
For a = 1 /xm and d = 10 nm the retarded
sphere-plate interaction energy is less than
half of the unretarded value.
(c) The expression of Czarnecki, Eq. [12],
gives excellent agreement with the Clay-
field results at all separations except be-
low about 5 nm, where it gives values
which are much too high.
(d) The modified interpolation formula,
Eq. [19], is an adequate approximation
for all separation distances up to about
d = a/5. (Because of the fitting procedure,
agreement with the Clayfield results is exact
at d = a/10).
(e) Equation [14] is a good approximation
up to about d = a/10, but becomes inac-
curate at larger separations.
CONCLUSIONS
In seeking a convenient approximation
for practical purposes it is only necessary
Journal of Colloid and Interface Science, Vol. 83, No. 1, September 198t
JOHN GREGORY
[19]
\
a(nm}
FIG. 4. T h e effect of retardation on the interaction
of a sphere, radius 1/zm, with a semi-infinite fiat plate.
Calculations based on: (1) T h e full, unretarded Ha-
m a k e r expression, Eq. [17]. (2) The a p p r o x i m a t e unre-
tarded H a m a k e r expression, Eq. [18]. (3) T h e " e x a c t "
retarded results of Clayfield et al. (13). (4) T h e ex-
pression of Czarnecki, Eq. [12]. (5) T h e modified
interpolation formula, Eq. [19], and ;t = 100 nm. (6)
The n e w approximation, Eq. [14] with a2 = ~,
b = 5.32, and )t = 100 nm.
that the results should be accurate where
the interaction is large enough to be
significant. Since Hamaker constants for
colloidal dispersions rarely exceed 5kT
(2 x 10-20 J), the interaction energy be-
comes insignificant relative to the thermal
energy of the particles when V/A is less
than about 0.1. Inspection of Figs. 2-5
shows that the retarded interaction energy
falls to below this value before the geometric
restriction, d ~ a, begins to cause serious
inaccuracies in the short-range approxima-
tions. Consequently, because of their
greater simplicity, the short-range expres-
sions are likely to be acceptable ap-
proximations.
For most practical problems, retarded
interaction can be represented by the ap-
propriate unretarded Hamaker expression
modified by a simple correction factor,
which depends on the separation distance
and the characteristic wavelength.
 VAN DER WAALS INTERACTION 145

sphere radius. At greater distances, the

interaction will usually be insignificant, but
if computations have to be carried out in
this region the Czarnecki expression, Eq.
[12], can be used. This must not be used for
interaction at close approach.
In calculating van der Waals interaction
for fairly large particles (1 /zm or greater)
neglect of the retardation effect leads to a
serious overestimate of the interaction,
even at separation distances of only a few
nanometers. The use of very simple ap-
proximations for retarded interaction, such
as Eq. [19], requires hardly any more ef-
lO d ( n m / lOO 2o0
fort and gives greatly improved results.
FIG. 5. Same as for Fig. 4, but with the sphere
radius 100 nm. REFERENCES

1. Hamaker, H. C., Physica 4, 1058 (1937).

For the interaction of plates, Eq. [8] with
b = 5.32 is an adequate representation of
the two Overbeek expressions, Eqs. [5]
and [6].
Retarded interaction between spheres can
be adequately approximated by the simple,
short-range, Hamaker expression, Eq.
[10], together with a correction factor.
This factor can take the form given in
Eq. [11] or in Eq. [14]. While the latter
gives somewhat better agreement with exact
results (and might be still further improved
by adjustment of the constant b), the simple
interpolated formula, Eq. [11], may be good
enough for most purposes. Both of these
approximations become better as the par-
ticle size increases.
For the important sphere-plate case simi-
lar remarks apply, but here the short-
range Hamaker expression, Eq. [18], with a
suitable correction factor, gives even better
agreement with exact results. In this case,
the factor given in Eq. [19], can be used
up to separations of about 20% of the
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Journal of Colloid and Interface Science, Vol. 83, No. 1, September 1981