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Colloidal diffusion in confined geometries

Cite this: Phys. Chem. Chem. Phys.,
2017, 19, 23632
Received 18th April 2017,
Accepted 19th May 2017
DOI: 10.1039/c7cp02497e
rsc.li/pccp
Kim Nygård
Colloidal dispersions in confined geometries exhibit rich diffusive dynamics governed by an interplay
between particle–particle and particle–wall interactions. This perspective reviews recent selected
computational and experimental studies on diffusion of dense liquid-like dispersions in spatial
confinement, with an emphasis on general physical concepts rather than system-specific details. The
common thread is to analyse colloidal diffusion in confined geometries in terms of the local density
experienced by the colloidal particles, viz. at the level of anisotropic pair densities, which have recently
become experimentally accessible.

1 Introduction to bulk;3 diffusivities, relaxation times, and viscosities may change

by orders of magnitude once a molecular liquid is confined on
It is well documented that nanoscopic confinement induces the nanometre scale. The mechanistic understanding of such
ordering of molecular liquids, which in turn strongly alters their scientifically intriguing confinement phenomena, and their use in
properties and even induces emergent phenomena.1 An early technological applications,4 has been an active area of research
textbook example is the phenomenon of oscillatory solvation for several decades.
forces between suspended surfaces;2 the degree of molecular Spatially confined colloidal dispersions exhibit many simi-
order between the suspended surfaces, and hence the pressure larities with nanoscopically confined molecular liquids, such
in the gap, depends on the surface separation, leading to an as confinement-induced microscopic ordering and ensuing
oscillatory solvation force between the surfaces as a function of oscillatory solvation forces.5 In terms of dynamic properties,
their separation. Another prominent feature of nanoscopically however, there are prominent differences between molecular
confined liquids is their markedly different dynamics compared liquids and colloidal dispersions. Notably, colloidal dynamics
is affected not only by direct particle interactions, but also by
Department of Chemistry and Molecular Biology, University of Gothenburg,
indirect, hydrodynamic interactions mediated by the solvent.
SE-41296 Gothenburg, Sweden. E-mail: kim.lj.nygard@gmail.com The resulting rich colloidal dynamics has been extensively
studied in bulk, as is evident from the comprehensive review
of ref. 6. Confining walls further complicate matters, and at the
Kim Nygård earned his PhD in moment colloidal diffusion in confinement is an active area of
experimental materials physics research.
in 2007 from the University of Colloidal dynamics in confined geometries is a broad topic.
Helsinki, Finland. After post- I have therefore decided to concentrate on a few selected
doctoral positions at the Paul scientific questions, focusing on general physical concepts
Scherrer Institut, Switzerland, rather than system-specific details. First, I only discuss diffusive
and the European Synchrotron dynamics of the colloidal particles in the absence of macroscopic
Radiation Facility, France, he density gradients, disregarding the much faster solvent dynamics.
took in 2011 up a position as Second, and most important, I concentrate on diffusion of dense
assistant professor at the colloidal dispersions confined between walls at a separation
University of Gothenburg, Sweden. of a few particle diameters, where the correlation between
In the summer of 2017 he will join confinement-induced microscopic ordering and colloidal diffusion
Kim Nygård the MAX IV Laboratory, University is prominent. I will not discuss closely related phenomena such as
of Lund, Sweden. During the last single-file diffusion7,8 the crossover from three- to two-dimensional
years his main research interest has been the microscopic structure, dynamics,9 or confinement-induced particle trapping.10 Finally, for
dynamics, and ensuing properties of soft matter at interfaces and in simplicity I only discuss rigid spherical particles dispersed in
spatial confinement. liquids, which are confined between planar solid walls, thereby

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neglecting e.g. diffusion of colloidal dispersions in mesoporous
matrices.11 Nevertheless, the concepts brought up may have a
broader range of application.
I am not the first one to review the dynamics of dense fluids
in confined geometries. For another recent example, I refer to
ref. 12. Here I therefore take a different angle. The temporally
averaged short-range neighbourhood of a colloidal particle is
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described in terms of the colloid’s pair density, or solvation
shell in the language of physical chemistry and chemical
physics. In stark contrast to bulk, dense confined fluids exhibit
anisotropic pair densities due to additional packing constraints
imposed by the confining walls.13–17 The common thread in
this perspective will thus be to discuss various aspects of
colloidal diffusion in confined geometries at this fundamental
level of anisotropic pair densities.
The rest of this perspective is organised as follows. In
Section 2 I briefly define the microscopic structure and dynamics
of confined colloidal dispersions, at the level of anisotropic pair
densities. In Sections 3 and 4 I discuss self- and wave-vector-
dependent diffusion of colloidal dispersions in confined geometries,
respectively, emphasising their analysis at the level of pair densities.
Finally, in Section 5 I summarise the take-home messages of this
perspective and provide a brief outlook.
2 Microscopic structure and dynamics
Let me begin by a brief comment about the confinement
geometry. For conceptual clarity I will only consider the simplest
conceivable case – two parallel planar and smooth solid walls at a
separation H, as shown schematically in Fig. 1. In this geometry
the colloidal dispersion exhibits planar symmetry, and to simplify
the notation I will keep the central particle in the in-plane origin
when discussing pair properties. I denote the directions parallel
and perpendicular to the confining walls by R and z, respectively,
and the corresponding wave vector components by q|| and q>.
2.1 Static pair density
Consider next a colloidal dispersion confined between solid
planar walls at a short separation of a few times the particle
Fig. 1 Schematic of the confinement geometry, with two parallel planar
and smooth solid walls separated by a distance H. The particles’ centres are
thus confined to the region H–s between the walls, where s denotes the
particles’ diameter. The z axis is oriented normal to the confining walls, and the
parallel direction is denoted by R. Wave vector components parallel and
perpendicular to the confining walls are given by q|| and q>, respectively.
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Fig. 2 Schematic of a dense colloidal dispersion confined between planar
solid walls at close separation of a few times the particle diameter. The
confinement-induced microscopic ordering of the particles is, in the first
approach, quantified by their density profile n(z) across the slit, as shown to
the right. The yellow sphere depicts a tagged or central particle, depending
on whether I discuss self- or wave-vector-dependent diffusion,
respectively.
diameter, as schematically presented in Fig. 2. Here the colloidal
particles are depicted as spheres, while the solvent is only
implicitly assumed. The confining walls impose packing con-
straints on the particles, leading to their confinement-induced
microscopic ordering;18 in the schematic figure the particles
order into three layers parallel to the confining walls. The
microscopic ordering is usually characterised in terms of the
particles’ ensemble-averaged number density profile n(z) across
the confining slit, as shown to the right. An obvious question
then emerges: how does the microscopic ordering modify the
fluid’s diffusive properties?
It is important to realise, however, that while the density
profile n(z) describes the distribution of particles across the
confining slit, it does not describe the local distribution of
particles around a given particle. The ensemble-averaged local
density around a central (or tagged) particle, say the yellow
particle in Fig. 2, is instead given by the pair density n(r1)g(r,r1),
where g is the pair distribution function, r the central particle’s
position, and r1 the position where one measures the local
density.† Since ng describes the local distribution of particles
experienced by the central particle, and hence provides means
to describe the central particle’s pair interactions, it is a
physically appealing starting point for analysing colloidal
diffusivity in confined geometries.
I emphasise that the pair density ng is a fundamental quantity
for understanding the properties of dense fluids, providing a
formal relationship between the fluid’s microscopic interactions
and its macroscopic properties. Moreover, it is experimentally
accessible in terms of the structure factor by scattering of
neutrons, X-rays, or light, allowing quantitative comparison
between experiment, theory, and simulations at an advanced
level. The pair density is thus the most important quantity for
characterising bulk fluids.19 However, due to the complexity of
ng in confined geometries compared to bulk, as shown below,
† In the present geometry n(r1)g(r,r1) simplifies to n(z1)g(z,z1,R12), where z and z1
denote the perpendicular components of r and r1, respectively, and R12 the
parallel component of |r  r1|.
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confined fluids are only rarely analysed at the level of pair

densities.13,14,17,20,21 Nevertheless, computational studies on
confined fluids at this fundamental level have become more
common in recent years, including ion–ion correlation effects
in confined electrolytes,22 depletion interactions,23 tuneable
assembly of charged confined fluids,24 the glass transitions in
confined geometries,25 ordering mechanisms in confined
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fluids,16 and fluid inclusions in porous matrices.26 From an

experimental point of view, in turn, we have very recently
developed unique methodology for studying pair densities of
confined fluids in terms of structure factors, based on X-ray
scattering from colloid-filled micro- or nanofluidic channels.27–29
For a brief recent review on pair densities in confined fluids,
see ref. 30.
In Fig. 3 I exemplify the theoretical pair density ng for a
hard-sphere fluid confined between hard planar walls.15 Here I
show a relatively dense fluid in a narrow slit, in order to
highlight the effects of confinement, but similar although less
prominent features are also observed at lower particle concen-
trations and larger separations between the confining walls.
The data exhibit two particularly important features. First, the
anisotropic packing in confined fluids shows up as strongly
anisotropic pair densities ng. Second, the confined fluid’s pair
density depends strongly on the central particle’s position in
the slit. Both of these features are in stark contrast to the pair
densities of isotropic and translationally invariant bulk fluids.
In terms of the topic of the present perspective, the strongly
anisotropic and position-dependent pair density ng implies
likewise strongly anisotropic and position-dependent diffusivity,
as will be discussed below.

2.2 Intermediate scattering function

The pair density ng discussed above describes a temporally
averaged microscopic structure, and is thus a static quantity.
Its ‘‘dynamic’’ counterpart is given by the so-called Van Hove
function,31 which describes the ensemble-averaged pair corre-
lations in both space and time. For my purposes it is conve-
nient to instead define the spatiotemporal pair correlations in
reciprocal space in terms of the intermediate scattering func-
tion F(q,t), where q is the wave vector characterising density
fluctuations and t the time. Formally the intermediate scattering
function is given by6,32

F(q,t) = N1hdnq(0)dnq(t)i, (1)

where N denotes the number of particles in the system, dnq(t)

a Fourier component of number density fluctuations of wave
vector q, and h  i an ensemble average. In essence, F(q,t) is a
temporally resolved structure factor.
A direct connection between the intermediate scattering
function and the static pair densities of Section 2 is obtained
in the limit t - 0, where we obtain the structure factor, F(q,0) =
N1hdnq(0)dnq(0)i  S(q). For confined fluids the structure
factor is given in terms of static density distributions as
ðð
1 density minimum, or (c) in the slit centre. Reprinted from K. Nygård et al.,
SðqÞ ¼ 1 þ nðrÞnðr1 Þhðr; r1 Þexp½iq  ðr  r1 Þdrdr1 ; (2)
N
Fig. 3 Anisotropic pair density n(z1)g(z,z1,R12) around a central particle,
calculated for a dense hard-sphere fluid confined between hard planar and
parallel walls at a short separation. The pair density is presented as a function of
position parallel (R12) and normal (z1) to the confining walls, and the grey region
depicts the excluded volume around the central particle. The confining wall
separation is H = 3.05s and the confined fluid is in contact with a bulk reservoir
of number density nb = 0.75s3 (bulk volume fraction fb E 0.39). The central
particle is positioned either (a) in contact with one of the confining walls, (b) in a
J. Chem. Phys., 2013, 139, 164701, with the permission of AIP Publishing.

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Fig. 4 (a) Anisotropic structure factor S(q) for the confined hard-sphere
fluid of Fig. 3, shown as a function of wave vector components parallel (q8)
and normal (q>) to the confining walls. (b) Corresponding isotropic bulk
structure factor as a function of wave vector magnitude q.
where h(r,r1) = g(r,r1)  1 denotes the total pair correlation
function and the integrals are carried out over the space
between the confining walls.‡ For convenience I exemplify in
Fig. 4 the structure factor of a dense fluid both in bulk and in
narrow confinement; whereas the isotropic bulk fluid exhibits
an isotropic structure factor, the strongly anisotropic pair
densities of the confined fluid, as seen in Fig. 3, shows up as
a strongly anisotropic structure factor.15 Similar as for the
confined fluid’s anisotropic pair density ng discussed above,
the anisotropic structure factor S(q) implies anisotropic
diffusivity.
An important feature of the intermediate scattering function
F(q,t) and the structure factor S(q) of eqn (1) and (2), respectively,
is that they are directly accessible in scattering experiments. The
former can be accessed, in terms of the normalised intermediate
scattering function f (q,t)  F(q,t)/S(q), via temporally resolved
scattering experiments such as dynamic light scattering (DLS) in
the optical regime33,34 or X-ray photon correlation spectroscopy
(XPCS) in the X-ray regime.35,36 The latter, in turn, can be probed
via temporally averaged scattering experiments, such as static
‡ For isotropic and translationally invariant bulk fluids eqn (2) simply yields the
isotropic S(q) = 1 + nbh(q), where q = |q| and h(q) is the Fourier transform of the
isotropic total pair correlation function.19
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light scattering (SLS) using optical light6 or small-angle X-ray
scattering (SAXS) using X-rays.37,38 In fact, we have recently
demonstrated the feasibility of SAXS and XPCS from colloid-
filled micro- and nanofluidic containers, thus allowing us to
probe experimentally the microscopic structure27–29 and diffu-
sive dynamics39 of confined colloidal dispersions at the level of
anisotropic pair densities.
The intermediate scattering function is a complicated quantity,
which contains a wealth of information on colloidal structure and
dynamics. Before I proceed with selected examples of colloidal
diffusion in confined geometries, I will therefore briefly mention a
few limiting cases of F(q,t):
 In the general case, F(q,t) is sensitive to collective
dynamics at length scales comparable to the reciprocal of the
wave vector. In such wave-vector-dependent diffusion, the local
density around a central particle, say the yellow sphere in Fig. 2,
relaxes due to the motion of all particles in the confined
system.
 For large wave vectors the contributions to F(q,t) from
distinct particles cancel out, and the data are dominated by
single-particle dynamics. In this limit one probes self-diffusion;
one focuses on a tagged particle, for example the yellow sphere
in Fig. 2, and follows its diffusion in the presence of the other
particles in the system and the confining walls. In practice this
limit is reached when q c qm, where qm is the position of the
primary peak in the structure factor S(q), such that S(q) has
essentially decayed to unity. In the case of Fig. 4(a), this limit
would be reached for q c 2ps1.
 In the limit of short wave vectors, q { qm, F(q,t) probes
collective diffusion at length scales much larger than the
colloidal particles’ size (or any other characteristic length of
the system).
In the following I will consider these different cases in more
detail.
3 Self-diffusion
Colloidal self-diffusion typically falls into three time regimes.6,32
In the short-time limit, t { s2/4D0 with D0 denoting the Stokes–
Einstein diffusion coefficient, the tagged particle diffuses only a
small fraction of its size and the surrounding solvation shell has
essentially not changed. In this regime the central particle’s mean
square displacement (MSD) is linear in time. In the long-time
limit, t c s2/4D0, the tagged particle has had time to collide many
times with other particles, thus exhibiting long-distance ‘‘random
motion’’ and again a linear MSD. Finally, at intermediate times,
t E s2/4D0, the tagged particle exhibits retarded diffusion due to
interactions with the distorted solvation shell, showing up as a
sublinear MSD. In the next subsections I will focus on the long-
time limit.
The diffusive dynamics of colloidal dispersions at high
densities is governed by a complex interplay between direct
particle interactions and indirect ones mediated by the solvent.
The latter, hydrodynamic interactions are both long-ranged and
nonadditive, and hence their effect on colloidal diffusion is in
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general rather complicated.6,32 However, experiments imply
that hydrodynamic interactions may be negligible when con-
sidering self-diffusion in the long-time limit.40 Although the
following discussion on self-diffusion in confinement is largely
based on simulations containing direct particle interactions
only, the results should also be useful when predicting colloidal
diffusion in confined geometries.
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3.1 Slit-width-dependent self-diffusion
Let me first consider a colloidal dispersion confined between
planar solid walls, similar as depicted in Fig. 2, with a wall
separation H c s large compared to the characteristic length
scales of the colloid. In the vicinity of the solid walls the colloid
exhibits microscopic structure and diffusive dynamics different
from bulk, while in the slit centre it shows bulk diffusion. With
decreasing wall separation H the relative amounts of bulk and
interfacial colloid initially vary in a monotonic manner, and
accordingly the ensemble-averaged self-diffusion coefficient D
also varies monotonically. Colloidal diffusion in this regime of
large wall separation, sometimes coined weak confinement, is
thus governed by the single solid-fluid interfaces. For a brief
discussion of diffusion in weak confinement, see ref. 12.
For sufficiently narrow confinement, also known as strong
confinement, the wall-induced microscopic ordering of the
colloidal particles protrude throughout the confining slit.
In this regime the degree of ordering is governed by the
competition between the mutually incompatible preferred
packing of particles among themselves and the additional
packing constraints imposed by both confining walls.16 During
the last decade, extensive simulations on simple model fluids
have shown that this competition also results in nonmonotonic
confinement effects on colloidal diffusion.41–43
In Fig. 5 I exemplify the nonmonotonic self-diffusivity (blue
circles) for a dense hard-sphere fluid as function of confining
wall separation, obtained from simulations of ref. 41 and 43.
While these data were collected parallel to the confining walls,
qualitatively similar behaviour has been observed in the normal
direction.42 Intriguingly, the self-diffusion coefficient D8(H)
oscillates with increasing wall separation H – a first evidence
of nonmonotonic confinement effects on colloidal diffusion. I
emphasise that the volume fraction of particles in the slit was
kept constant in the simulations, i.e., the confined fluid was
not kept in equilibrium with a bulk reservoir, so the oscillatory
behaviour of D8(H) cannot be explained by simple density
arguments. I further note that the slit-width dependence of
D8(H) closely follows that of crystallisation44–46 and vitrification,12,47
implying that local particle packing is governing the diffusive
dynamics.
How can one rationalise this observation? Rosenfeld was the
first to note that in simple bulk liquids the diffusivity scales
with the excess entropy sex = s  sid,48,49 i.e., the difference
between the entropy of the system s and the ideal gas entropy
sid at the same thermodynamic conditions. As a further simplifi-
cation, the excess entropy is reasonably well approximated by its
two-body or pair contribution,50–52 which is given in terms of the
pair distributions. Thus one expects the bulk self-diffusivity D to
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Fig. 5 Dimensionless self-diffusion coefficient D8 parallel to the confining
walls of a dense hard-sphere fluid between planar hard walls, as obtained
from simulations. The blue circles depict D8 as a function of wall separation
H, when the average volume fraction of particles in the slit has been fixed at
f = 0.40. The green dashed line shows the bulk self-diffusion coefficient at
the same volume fraction. The red squares represent the self-diffusion
coefficient in bulk, determined at thermodynamic states where the excess
entropy sex equals the slit-width-dependent sex(H) of the confined fluid.
Data taken from ref. 41 and 43.
scale with the pair excess entropy sex
(2), a hypothesis which has been
found to hold for both atomic and molecular liquids.53–57 The
excess entropy scaling also seems to hold for colloidal dispersions
(at least over a limited range of particle concentrations), although
the exact interpretation in this case is still under debate.40,58
During the last few years this kind of excess-entropy scaling has
been extensively studied in terms of simple liquids’ so-called
quasiuniversality;59,60 many simple liquids have been found to
exhibit (nearly) invariant structure and dynamics along so-called
configurational adiabats, i.e., lines in the thermodynamic phase
diagram where the excess entropy sex is constant.
A series of simulation studies by Truskett et al. have shown
that the excess entropy sex indeed is a good predictor for
dynamics in confined fluids.41,43,61–63 The close connection
between self-diffusivity and excess entropy is also evident in
Fig. 5, where the red squares depict the bulk self-diffusion
coefficient determined by fixing the excess entropy at each
point to the slit-width-dependent sex(H) of the confined fluid.
The semi-quantitative agreement with the oscillatory diffusive
data of the confined fluid is striking. This observation implies
that local particle packing, as quantified by excess entropy sex
(or alternatively available volume43), also governs long-time
self-diffusion of colloidal dispersions in confined geometries.
The slit-width-dependent long-time self-diffusivity has also
been studied experimentally by confocal-microscopy-based particle
tracking of colloids between glass plates.64 Unfortunately, the wall
separations H in this study were relatively large, hindering the
observation of the predicted oscillatory diffusivity. Future experi-
mental verification of the intriguing oscillatory diffusivity and the
proposed entropy scaling would be an important advance in our
understanding of colloidal diffusion in narrow confinement.
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3.2 Position-dependent self-diffusion
So far I have discussed oscillatory self-diffusion as a function
of confining wall separation. However, since the local density
around a central (or tagged) particle depends on the latter’s
position in the slit, as seen in Fig. 3, one also expects position-
dependent diffusivity. This is indeed seen in simulations,
exemplified in Fig. 6 (red squares) as the position-dependent
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self-diffusivity D>(z) for a confined hard-sphere fluid normal
to the planar confining hard walls.42 The data exhibit two
prominent features. First, D>(z) is reduced near the impene-
trable confining walls, where the normal diffusion is limited to
one direction. Second, and more interesting, D>(z) oscillates
across the confining slit, and these oscillations in D>(z) nearly
coincide with the oscillations in the confined fluid’s density
profile n(z) (blue circles). Clearly, the data evidence a strong
correlation between confinement-induced microscopic ordering
and position-dependent self-diffusivity.
In bulk hard-sphere dispersions self-diffusivity decreases
with increasing particle concentration. Naively one would
assume that the same holds in confined geometries. How can
one then understand the counterintuitive positive correlation
between D>(z) and n(z) of Fig. 6, where a large local density
corresponds to a large local diffusivity? Following the reasoning
of Mittal et al.,42 the local particle insertion probability,13 and
hence the local available volume,65 is proportional to the
density profile n(z). Diffusing particles probe their neighbourhood
for available space and hence diffusivity should be roughly
proportional to the local available space, or to the density profile
as seen in Fig. 6.
A close inspection of Fig. 6 reveals a phase shift between
extrema in D>(z) and n(z), most notable around z = 1s. In line
with the discussion of Section 3.1, a local excess entropy may be
a better predictor of position-dependent diffusivity than the
Fig. 6 Microscopic structure and diffusion of a dense hard-sphere
fluid between planar hard walls, as determined by simulations. The blue
circles depict the density profile n(z) across the confining slit, while the red
squares denote the dimensionless local self-diffusivity D>(z) normal to the
confining walls. Data are shown for the wall separation H = 5.0s and the
average volume fraction f = 0.40 in the slit. Data taken from ref. 42.
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Fig. 7 Theoretical pair contribution to the excess entropy, determined for
the hard-sphere fluid of Fig. 3. (a) Position-dependent pair excess entropy
s(2)
ex (z) (red line) for a planar confining slit of width H = 5.0s, as determined
using eqn (3). The fluid’s density profile n(z) across the confining slit (blue
line) is shown for comparison. (b) Pair excess entropy s(2) ex (red circles) as
a function of confining slit width H, obtained as the weighted average of
s(2)
ex (z). The average number density nH in the slit (blue line) is shown for
comparison.
density profile. One possibility is the position-dependent pair
excess entropy,66
ðð
sex
ð2Þ ðzÞ ¼ pkB Rnðz1 Þðg ln g  hÞdz1 dR; (3)
where kB is Boltzmann’s constant, the integration is again
carried out over all space between the confining walls, and I
have used the shorthand notation g = g(z,z1,R) (and similarly for
h = g  1). The pair excess entropy discussed above is retained
Ð .Ð
as a weighted average, sex
ð2Þ ¼ nðzÞs ex
ð2Þ ðzÞdz nðzÞdz. In Fig. 7(a)
I plot the theoretical position-dependent pair excess entropy
s(2)
ex (z) calculated for the confined hard-sphere fluid of Fig. 3,
together with the corresponding density profile n(z). Indeed,
ex (z) around z E 1s are shifted towards the
the extrema in s(2)
slit centre compared to the extrema in n(z), in line with the
phase shift of D>(z) in Fig. 6. In the spirit of this perspective, it
would be interesting to quantitatively compare D>(z) and s(2) ex (z),
thereby characterising how accurately the confined fluid’s local
diffusivity is predicted by particle packing at the level of pair
densities.§
§ To the best of my knowledge, the connection between local pair excess entropy
of eqn (3) and local diffusivity of confined fluids has prior only been briefly
discussed in ref. 66.
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Recent simulation studies have shown a rich behaviour of
the position-dependent diffusivity.67 First, the self-diffusivity
D8(z) parallel to the confining walls does not show any dependence
of the particle’s position in the slit, in stark contrast to the normal
diffusivity D>(z). This observation has also been corroborated
experimentally by video microscopy on colloidal dispersions
confined between glass plates.64,68 Second, upon increasing the
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particles’ volume fraction to high densities, the positive correlation
between the normal diffusivity D>(z) and the number density
profile n(z) evolves into a negative one, with local maxima (minima)
in D>(z) approximately coinciding with local minima (maxima)
in n(z). To date no rationale for either the position-dependent
diffusivity or its concentration dependence has been proposed.
Let me close this subsection by returning to the slit-width-
dependent excess entropy sex of the confined hard-sphere fluid. In
Fig. 7(b) I present the theoretical pair contribution s(2) ex versus slit
width H for the system of panel (a). For comparison, I also show
the average particle number density between the confining walls,
Ð
nH ¼ H 1 nðzÞdz.15 In contrast to Fig. 5, where nH (and likewise
f) was kept constant, these data were obtained by keeping the
confined fluid in equilibrium with a bulk reservoir, resulting in a
slit-width-dependent nH. The data exhibit two prominent effects.
First, the general decrease in nH with decreasing slit width H is
accompanied by an increase in s(2) ex . Second, and more interesting,
we observe a phase shift between s(2) (2)
ex and nH versus H; sex exhibits
maxima (minima) for H slightly below integer (half-integer) multi-
ples of the particle diameter, while for nH these occur at larger H
values. Clearly, in confinement the pair excess entropy is not
directly proportional to the number of particles in the slit, as
would be expected in analogy with bulk, but depends instead more
subtly on particle packing at the level of pair densities via eqn (3).
4 Wave-vector-dependent diffusion
In the preceding section I discussed self-diffusion in the long-
time limit, with an emphasis on simulation studies. In the
remainder of this perspective I will briefly consider the extension
to wave-vector-dependent diffusion, which has recently become
experimentally accessible.39 I foresee that this approach in the
coming years also will provide means to experimentally corro-
borate the simulation-based predictions discussed above.
Wave-vector-dependent diffusion is in general a complicated
phenomenon, which I will not pursue here. Let me instead for a
moment focus on short times, where the analysis is simplified.
In this limit the wave-vector-dependent diffusion coefficient
D(q), which describes spatiotemporal density fluctuations of
wave vector q, retains the formally simple form6,32
HðqÞ
DðqÞ ¼ D0 : (4)
SðqÞ
Here D0 denotes the Stokes–Einstein diffusion coefficient of non-
interacting particles, S(q) the structure factor describing the effect of
direct particle interactions, and H(q) the hydrodynamic function¶
¶ For clarity I use different fonts to make a distinction between the hydrodynamic
function H(q) and the slit width H.
23638 | Phys. Chem. Chem. Phys., 2017, 19, 23632--23641
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describing the effect of indirect interactions mediated by the
solvent. Note that while eqn (4) has been derived in the short-
time limit, for bulk colloids the long-time diffusion has been
observed to exhibit almost the same wave-vector dependency
(apart from a scaling factor).69,70
The functional form of eqn (4) is physically appealing.
Density components corresponding to a maximum in S(q) are
favourable in terms of the interaction free energy and therefore
decay slowly. This inverse relationship between D(q) and S(q)
is sometimes referred to as ‘de Gennes narrowing’,71 in spirit
of early work by de Gennes on the dynamics of atomic and
molecular systems,72 although the underlying physics of
colloidal diffusion and atomic/molecular dynamics differ.73
It should be noted, however, that the simple form of eqn (4) is
conceiving, with the long-ranged and non-additive hydrodynamic
interactions rendering H(q) a rather complicated function.
In particular, while H(q) can be theoretically calculated with a
reasonable accuracy in bulk,74–76 the presence of walls have so
far hindered its theoretical analysis in confinement.
Note that the short-time wave-vector-dependent diffusion
coefficient D(q) and the Stokes–Einstein coefficient D0 can be
experimentally determined in photon correlation experiments
(DLS33,34 or XPCS35,36), whereas the structure factor S(q) can be
determined in the temporally averaged limit (SLS6 or SAXS37,38).
By combining these results one thus obtains access to the
hydrodynamic function H(q) via eqn (4). For bulk colloids this
is a standard approach,6 and it has also been applied to study
the diffusion of dense colloidal dispersions near single solid
walls by evanescent-wave DLS.77,78 For spatially confined dense
colloids, in turn, previous work has mainly concentrated on the
limiting cases of one- and two-dimensional fluids,7,8,79–81
rather than the strong confinement which is the focus here.
In the latter case a promising approach is to confine colloidal
dispersions in micro- or nanofluidic channel arrays, and use
X-rays for characterisation.82–85 We have recently extended this
approach for simultaneous experimental determination of the
static structure factor27–30 and the wave-vector-dependent diffusion
coefficient39 of dense colloidal dispersions in confinement. In the
following I will exemplify these novel results.
In Fig. 8(a) I present the structure factor S(q), collected from
a confined colloid in three directions with respect to the
confining walls.39 The structure factor exhibits strong aniso-
tropy similar to the data of Fig. 4(a); the primary peak in S(q) is
more prominent and shifted towards larger q values in the
intermediate direction (161 with respect to the confining walls)
compared to the parallel (01) and diagonal directions (451).
In panel (b) I present for comparison the inverse of the wave-
vector-dependent diffusion coefficient, D1(q). Most importantly,
the qualitative agreement between the data of panels (a) and (b)
corroborate the inverse relationship between D(q) and S(q) of
eqn (4), demonstrating the important contribution of direct
particle interactions on wave-vector-dependent diffusion.8
8 The data of Fig. 8(b) were not collected strictly in the short-time limit.39
However, very recent analysis in the short-time limit does yield a qualitatively
similar inverse relationship between D(q) and S(q).86
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Fig. 8 Anisotropic wave-vector-dependent microscopic structure and
diffusive dynamics of a confined colloidal dispersion, as determined in
X-ray scattering experiments on colloid-filled microfluidic containers. The
data were collected for a hard-sphere-like colloid confined between
planar solid walls at a separation of 2.7s, and the confined colloid was
kept in equilibrium with a bulk reservoir of volume fraction fb = 0.168.
(a) Structure factor S(q) and (b) inverse of the wave-vector-dependent
diffusion coefficient D(q) of the confined colloid, measured parallel to the
confining walls (01, red squares), diagonally across the confining slit (451,
blue circles), and in an intermediate direction (161, green asterisks). Data
taken from ref. 39.
The above discussion neglects the effect of indirect, hydro-
dynamic interactions. In bulk colloids the hydrodynamic particle–
particle interactions result in a hydrodynamic function H(q)
whose shape closely follows that of the structure factor.6 For
dense confined colloids one expects two complications. First,
hydrodynamic interactions between a central particle and its
anisotropic solvation shells (cf. Fig. 3) leads to anisotropic
ensemble-averaged hydrodynamic interactions, which in turn
should yield an anisotropic H(q) akin to the anisotropic S(q).
Second, it has been known for a long time that a single solvated
particle is slowed down by the presence of solid walls,87,88 an
effect which has been observed experimentally both at a single
planar wall89,90 and in confinement between two planar walls.91
One thus expects the hydrodynamic function H(q) of a dense
confined colloid to result from a convoluted combination
of anisotropic particle–particle and particle–wall interactions.
As an initial step, we have very recently analysed the data of
ref. 39 to obtain the first evidence of a strongly anisotropic
hydrodynamic function H(q), the shape of which is qualitatively
similar to that of the structure factor S(q).86 More experimental
and theoretical work is needed in order to understand this
phenomenon.
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5 Summary and outlook
In this perspective I have reviewed recent research on colloidal
diffusion in narrow confinement. The common thread has
been to analyse diffusion of confined colloids in terms of the
local density experienced by a tagged or central particle, namely
the anisotropic pair density. This approach highlights an
important take-home message of the present perspective –
colloidal diffusion in confinement can be analysed using the
same concepts as in bulk, provided one makes the effort to
describe the anisotropic pair densities.
Colloidal diffusion in narrow confinement has been studied
extensively during the last decade by means of simulations.
This research has brought into evidence a wealth of interesting
diffusion phenomena, such as slit-width-dependent and position-
dependent long-time self-diffusion reviewed here. A particularly
important finding is that these diffusive properties of confined
fluids correlate with the (pair) excess entropy, implying that the
dynamics can be predicted based on particle packing. In order to
obtain mechanistic insights beyond such correlations between
self-diffusion coefficients and excess entropies (or their position-
dependent counterparts), however, a first-principles microscopic
theory of confined colloidal dynamics would be highly useful.
A promising such candidate is the mode coupling theory,92 which
has recently been extended to confined geometries.47,93,94 Since
this theory also yields the confined fluid’s intermediate scattering
function,95 it should provide means for quantitative comparison
with experiments.
An important point of this perspective is that we now have
experimental access to confined colloids’ structure factors and
intermediate scattering functions, via X-ray scattering from
colloid-filled microfluidic containers.28,39 So far this approach
has been used to demonstrate an inverse relationship between
the confined colloid’s wave-vector-dependent short-time diffusion
coefficient and anisotropic structure factor, as discussed above.
At the moment, it will allow us to address many important
questions related to colloidal diffusion in confined geometries,
ranging from the effect of hydrodynamic interactions to structural
arrest. With the advent of extremely brilliant sources,36 however,
I also foresee that these studies are extended to large wave vectors,
and hence self-diffusion. The possibility to simultaneously probe
the confined colloid’s pair densities (via its anisotropic structure
factor) and its long-time self-diffusion coefficient will provide
unique means to experimentally corroborate the aforementioned
correlation between slit-width-dependent self-diffusivity and
(pair) excess entropy.
I have in this perspective focused on the microscopic
structure and diffusive dynamics of archetypical hard-sphere-
like colloids confined between planar hard walls. The concepts
brought up may have a broader range of application, however, as
alluded to already in the introduction. Of particular interest is the
common system of charge-stabilised colloids between charged
walls. These systems exhibit qualitatively similar microscopic
ordering, at the level of anisotropic pair densities,27 as the hard-
sphere fluid between hard walls. One may thus anticipate that
charged colloids in confinement also will exhibit qualitatively
Phys. Chem. Chem. Phys., 2017, 19, 23632--23641 | 23639

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similar diffusive properties as discussed above, although this
hypothesis needs to be corroborated in future studies.
Acknowledgements
I thank Jeetain Mittal, Gaurav Goel, and Thomas M. Truskett
Published on 19 May 2017. Downloaded by Nanyang Technological University on 9/15/2019 12:23:06 PM.
for sharing their simulation data, and Roland Kjellander for
comments on the manuscript. I am grateful to the Ruth and
Nils-Erik Stenäck foundation for financial support.
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