Colloids and Surfaces A: Physicochemical and Engineering Aspects 206 (2002) 241 251 www.elsevier.

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Wetting of nanoparticles and nanoparticle arrays

C. Powell, N. Fenwick, F. Bresme, N. Quirke *
Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington SW7 2AY, UK

Abstract We report investigations of nanoparticulate wetting carried out using molecular dynamics simulations. Despite their small size, model LennardJones nanoparticles in simple Lennard Jones solvents exhibit well dened contact angles, which for high surface tension interfaces have been shown to obey Youngs equation with surprising accuracy. In this paper we present new results for fully molecular models of nanoparticles at a water surface, where again well-dened contact angles are evident. Pressure area curves obtained in Langmuir trough experiments on (nano) particulates have been used in the past to determine contact angles. We have recently demonstrated by molecular dynamics and theory that, contrary to expectations, the collapse pressure measured in this experiment should be independent of contact angle and that the initial collapse mode is by surface buckling. We present new molecular dynamics results for arrays of nanoparticles with a contact angle of 72 at a liquid vapour interface which conrm our earlier work and offer more information on the details of the structure of collapsed nanoparticle arrays. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Surface tension; Nanoparticles; Wetting

1. Introduction Three phases in contact exhibit a range of interesting behaviour. For example in the case of a solid in contact with liquid and vapour it is possible to distinguish two cases: one where the liquid forms a uniform (macroscopic) lm covering the solid surface, the complete wetting state and a second where the liquid forms a droplet on the surface, partially covering the surface, the partial wetting state. For a solid particle in contact with two bulk uid phases, the completely wet (or dry) phase corresponds to the particle
* Corresponding author. E-mail address: n.quirke@ic.ac.uk (N. Quirke).

being completely immersed in one phase whilst the partially wet state has the particle sitting in the interface between the two uid phases. Such states and the transitions between wetting states are of both scientic and industrial interest, for example in determining the order of wetting transitions or in tailoring wetting properties for high speed printing or emulsion stabilisation. Currently there is very strong interest in the description of wetting of nanoscale materials and of nanostructured/nanopatterned materials. Examples include the behaviour of nanoparticles at uid interfaces and its connection to self-assembly [1], the wetting of micron-sized channels [2] or nanopores for the formation of nanowires [3], and the wetting of nanoscale patterned interfaces with application to nanolithography.

0927-7757/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 7 7 5 7 ( 0 2 ) 0 0 0 7 9 - 1

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In this paper we report investigations of nanoparticulate wetting carried out using molecular dynamics simulations. In previous work [4 6] we have shown that despite their small size, model LennardJones nanoparticles in simple Lennard Jones solvents (at both liquid vapour, LV and liquid liquid interfaces) exhibit well dened contact angles, which for high surface tension interfaces (in particular the liquid liquid case) have been shown to obey Youngs equation with surprising accuracy. Our initial results [4 6] were for a LV interface with a surface tension of 3 mN m 1 (using LJs units for argon), which is low compared with the water/air surface tension, 72 mN m 1 but larger than say a microemulsion oil interface 0.1 mN m 1. By measuring the free energies of the simulated uid and solid interfaces we were able to show that Youngs equation is accurate for this interface for nanoparticles of diameter E3 nm. For smaller nanoparticles Youngs equation was less accurate and the simulations showed a wetting transition at 1 nm not predicted by Youngs equation. Youngs equation disregards one of the four interfaces in the system: the fourth interface being the line that separates the three phases. The free energy associated with this line, the line tension (~), may inuence the contact angle. We estimated [4 6] ~ from our simulations and found it to be of the order of 10 12 N. The effect of the line tension on the wetting properties of the nanoparticle, such as the contact angle, may be considered through a corrected Youngs equation, that reduces to the Youngs equation when ~=0 or 1/R 0 i.e. the curvature of the three phase line is negligible. Our data [4 6] show that the corrected Youngs equation is more accurate, but still breaks down for the smallest nanoparticles ( 1.5 nm). The situation may be different however for interface with a high surface tension. To investigate this question we simulated [4 6] nanoparticles at a liquidliquid interface for which the two liquid phases are immiscible, analogous to the water/oil interface. In this case the surface tension of the liquidliquid interface was 14 mN m 1 (compared to 3 mN m 1 for the LV case described above). We analysed the accuracy of

Youngs equation in this case by varying one of the surface tensions, kpf, keeping the other two constant. Youngs equation predicts the contact angle is a linear function of the surface tension. We found Youngs equation to be very accurate in predicting the wetting behaviour of the nanoparticle at this interface (k= 14 mN m 1) even for diameters approaching 1 nm. This contrasts with the results obtained for the LV interface. It might be that the line tension in these systems is negligible compared with the LV case. However our calculations [46] show that this is not so, indeed it is larger by one order of magnitude at 10 11 N. This can be understood by looking at the corrected Youngs equation, which predicts that the contact angle is a strong function of the line tension only when the surface tension of the uid uid interface is low. When the surface tension is high the contact angle is insensitive to line tension. From our studies [46] of model LJs nanoparticles at LJs interfaces we conclude that it is possible to describe the wetting of nanoscale interfaces (down to 1 nm) using Youngs equation when (a) the uid uid interfacial tensions are large and (b) the three phase line has a small curvature. These general results have been obtained using idealised structureless model nanoparticulates. In nature however nanoparticles have internal and surface structures, are not necessarily rigid and the solvents may themselves be complex. For example metal nanoparticles have received considerable attention during recent years due to the wide range of potential technological applications. These range from the use of dextran coated iron clusters [8] in target specic magnetic resonance imaging [9], to the use of lattices of organothiol stabilised gold clusters as chemical vapour sensors [10] and lithographic masks [11]. Particular interest has been shown in colloidal gold as a catalyst, especially since supported gold nanoparticles have been used to catalyse the oxidation of carbon monoxide [12]. In this paper we extend our work by describing a realistic molecular model of a thiol passivated gold nanoparticle at a water interface and reporting preliminary molecular dynamics simulations of its wetting properties. In the nal section we move from individual particles

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to nanoparticle arrays and consider the pressure area curves obtained in Langmuir trough (LT) experiments on such arrays. Since its original conception by Pockels [13] in the late 19th century and subsequent renement by Langmuir [14] in the 1920s the LT technique has become an important experimental tool in elds, ranging from biology to electronics. Surface pressure (P) area (A) isotherms obtained from LT experiments can provide important data on the geometry and intermolecular forces [15 18] of a wide range of materials. This includes the characterisation of nanoparticles used in processes relevant to oil recovery, otation, anti-foaming, gas sensors, biosensors pyro, piezo and ferroelectric dielectrics and has often involved the determination of contact angles and line tensions [19 21]. Such characterisations depend on the correct interpretation of the pressure area isotherm. We consider our recent molecular dynamics simulations and theoretical work [22] that, contrary to expectations, shows the collapse pressure measured in this experiment should be independent of contact angle and that the initial collapse mode is by surface buckling. We present new molecular dynamics results for arrays of nanoparticles with a contact angle of 72 at a LV interface which conrm our earlier work and discuss the details of the structure of the collapsed nanoparticle arrays.

potential whose nite range and depth is independent of the particulate diameter (Fig. 2 and Eq. (1)). Thus even for an innite diameter, where the particulate represents a planar structureless wall, the interaction with the uid is the same. This produces a clear separation between geometric and energetic effects. The spline potential has the form
Uij = |f 12 |f 6 4m ij r sij r sij m [a(r s r )2 + b(r s r )3] ij ij c ij c 0

    n

0B rsij B rs rs B r sij B rc rc B r

(1) where r is the separation between particles of species i and j, and |f is the diameter of the uid particles. The other variables for the LJ/S potential are dened as follows: rs = (26/7)1/6, rc = (67/48) r, a= ( 24192/3211)/r 2, s b=( 387072/61009)/r 3, s sff = 0 and sfp = (|p |f)/2. In the second case the uid uid, and uid nanoparticle interactions were modelled using LennardJones potentials, with a cutoff at 2.5|f. Note that now the uid nanoparticle interaction is stronger than the uid uid interaction. Using the model described above we performed molecular dynamics simulations of particulates at LV interfaces. For the present work a key quantity is the contact angle the particulate makes with

2. Results

2.1. LennardJones nanoparticles at innite dilution at uid interfaces

We consider the use of molecular simulation [23] to probe the wetting of nanoparticles at innite dilution in a uid interface. The situation of interest is displayed in Fig. 1. We consider particulates at uid interfaces with diameters in the range 1 nm upwards. In order to obtain general results we have dened idealised nanoparticles using both LennardJones spline (LJ/S) and Lennard Jones potentials as shown in Fig. 2. In the rst case the particulate interacts with the Lennard Jones atoms forming the uid phases through a LJ/S

Fig. 1. The system of interest, a particulate (labelled 1) diameter | at a uid interface, distance d from the uid interface, with contact angle q.

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Fig. 2. (a) The LJ/S potential, (b) the Lennard Jones potential for uid uid, uid colloidal nanoparticle, colloidal nanoparticle colloidal nanoparticle interactions.

the liquid phase. At any instant of time the surface is discharged on the atomic scale; in addition the particulate moves in and out of the (instantaneous) uid interface during the simulation [24]. Our concern in the present work is however, not with the uctuation properties of the particulate/ uid interface system (interesting as they are), but with the thermodynamic properties which arise from averaging the system. Thus we dene a contact angle using the average height d of the particulate as a function of time, with respect to the (average) LV equi-molar dividing surface. The time average of the quantity d is then related to the contact angle q (Fig. 1) using cos q = 2d/ |p. The contact angle dened in this way is consistent with that estimated from Youngs equation as discussed in Section 1. That a (time averaged) contact angle exists on the nanoscale can be seen from density proles taken across the interface with respect to the particulate centre of mass (Fig. 3). The proles were calculated by considering a

cylinder of radius r and length x centered on the particulate: z(x,r)= n(r, x)/6 here n(r, x) is the average number of solvent molecules in a shell of thickness dx= 0.2|f, with dr= 0.15|f, with volume 6 =2prdxdr. The gure shows a particulate with |p = 10|f (mfp/mff = 1.5) in a LJ/S LV interface at T*= 0.75 for which k*= 0.17 (stars refer to the usual LennardJones units). The contact angle is 90. The variation of contact angle with particle size and interaction strength has been described in detail for this system elsewhere [47]. In Section 3 we will also discuss LJ/S particulates with |p = 8|f, mfp/mff = 1.25, at T*= 0.5 (z* = 0.83, z* = 0.002, k*= 0.58) for which the l 6 contact angle is 1019 3. For the Lennard Jones system (Fig. 2(b)) with |p = 7|f, mfp/mff = 2, molecular simulations at T*=0.75 of a particulate in the LV interface (z* = 0.76, r* = 0.012, P*= l 6 0.008, k*= 0.49) produced a contact angle of 75.

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2.2. Molecular models of passi6ated gold nanoparticles at innite dilution at a water/air interface
In this section we report preliminary results for a molecular model of a gold nanoparticle at a water interface. Thiol passivated gold nanoparticles are described by a truncated octahedral (OT) motif and can be specied by indices (n,m) where n is the number of atoms along any edge which joins two (1 1 1) faces and m the number along any edge joining (1 1 1) and (1 0 0) faces [25]. Our cluster consists of a face centred cubic lattice of 140 atoms, adopting the OT morphology with

n= 4 and m= 2. In our calculations, we use the semi-empirical many body SuttonChen [26] potential parameterised for gold [27]. Ui (r)= m

where pi = %
j

    n 
a r
n

C
pi 2

a rij

(2)

the rst term represents the repulsion between atomic cores and the second term, pi, is the local density of atoms. The parameters m, a and C are determined by equilibrium lattice parameters and lattice energies. The exponent pairs, n and m are tted to elastic constants. For gold, m= 9.383265 kJ, a=4.080A, n= 10.0, m= 8.0 and C= 34.408 [28]. In order to maintain the OT structure in the passivated cluster the value of m was increased by a factor of 5 (see below).

2.2.1. The surface coating of the gold particle The potentials used to model the interactions between the gold, sulphur and alkyl chains can be divided into bonded and non-bonded interactions. The thiol chains were modelled using united-atom potentials [29] the potential functions and parameters used for describing the bonded interactions [3032] are shown in Table 1. For the molecular dynamics simulations of the passivated gold cluster we used the code DLPOLY, [33]. For computational convenience in using DLPOLY, the bonded interaction between the gold and the sulphur [34] was approximated as a nonbonded Morse potential [35].
U(r)= E0 r m 0 (nm) r

    n
n

r0 r

(3)

Fig. 3. Density prole of a LJ/S nanoparticle at the LV interface. The gure shows a particulate with |p = 10|f (mfp/ mff = 1.5) in a LJ/S LV interface at T*= 0.75 for which k*= 0.17 (stars refer to the usual Lennard Jones units). The contact angle is 90. Only the surface region of the liquid phase immediately surrounding the nanoparticle is shown, the greyscale variations show local density oscillations around the nanoparticle extending down into the bulk liquid. As we move from bottom to top across the LV interface (on the right and left hand sides of the nanoparticle) the density falls until we reach the vapour phase.

, with E0 = 38.594 kJ, n= 8, m=4, r0 = 2.9 A. Standard non-bonded interactions were modelled with a LennardJones 12-6 potential [36]. The appropriate parameters are shown in Table 2. Parameters for unlike interactions were obtained using LorentzBerthelot combining rules.

2.2.2. Cluster preparation The thiol passivated gold cluster was prepared using the method of Luedtke and Landman: [35].

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Table 1 Potentials and parameters for describing carbon chain bonded interactions Interaction Constrained bond Potential functions None, the bonds were constrained to a single, rigid length Atom types CH2 CH3 CH2 CH2 CH2 SH Harmonic angle Ubend(qi )= 0.5k(uiu0)2 CH2 CH2 CH3 CH2 CH2 SH Dihedral angle Utorsion(I)= 1 a1(1+cos )+1 a2(1cos(2i ))+1 a3(1+cos(3i )) 2 2 2 Parameters , r =1.54 A , r =1.54 A , r= 1.82 A Kq =519.73 kJ q0 =114.4 Kq =519.73 kJ q0 =114.4

CH2 CH2 CH2 SH a1 =5.9046 CHx CH2 CH2 CH2 a2 =1.134 a3 =13.1608

The bare, frozen, gold cluster was placed in a solution of butanethiol molecules and the system was allowed to equilibrate by molecular dynamics (1 500 000 timesteps, 1.5 ns) at low temperature (200 K), allowing an excess of butanethiol to absorb onto the gold surface. The temperature was then raised to 500 K in steps of 50 K (all 25 000 timesteps, 0.025 ns) allowing desorption of excess butanethiols and exploration of absorption sites, so that the thiols were absorbed on the gold surface in an HCP structure with 62 molecules absorbed in total, in good agreement with other work [37]. The butane of the butanethiol was then replaced by dodecane and equilibrated (all 500 000 timesteps, 1.25 ns). The gold atoms were kept frozen throughout, resulting in a surface annealed cluster without the structure of the gold nanoparticle being changed. However on unfreezing the gold the passivated cluster melted (the bare cluster was microcrystalline at all temperatures considered here). Due to the non-local nature of our Au S bond potential the sulphur atoms enter the gold cluster. By increasing the AuAu interactions (scaling m by a factor of 5) we forced the Au cluster to remain crystalline and the sulphurs bonded at the surface. The modied passivated Au nanoparticle was then equilibrated.

potential [38]. The interface was constructed by using a starting conguration comprising a liquid slab of 500 (and also 1000) water molecules in a simulation cell with vacuum on either side and equilibrating for 50 000 timesteps (or 0.125 ns) at 298 K. The surface tension was determined [23] by integrating the difference between the normal and tangential pressures across the interface giving a value of 649 5 mN m 1, 10% smaller than the experimental value [39] of 72.75 mN m 1 at 298 K.

2.2.4. Introducing the particle to the interface The passivated gold cluster was placed just above the water interface and its trajectory followed at 298 K for 325 000 timesteps (0.8125 ns). Fig. 4 plots d, the position of the gold centre of mass with respect to the average interface, the particulate settles down to a position approximately 1.5 nm above the mean interface. The contact angle is given by cos q= d/R, so that given R, it can be estimated from the gure (see below).
Table 2 LennardJones parameters for non-bonded interactions , | (A) CH3 CH2 SH Au 3.930 3.930 4.450 2.737 m (kJ) 0.9478 0.3908 1.6629 3.2288

2.2.3. The water liquid/6apour interface The water molecules in the water interface were modelled using the extended simple point charge

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Fig. 4. Height of the centre of mass of the gold core of the nanoparticle from the water interface (equimolar surface) as a function of time at 298 K.

For a exible nanoparticle the value of the radius R uctuates as the thiol molecules move in response to thermal uctuations. Fig. 5 is a density contour plot obtained in a similar manner to Fig. 3, for the passivated gold nanoparticle at a water interface. The nanoparticle clearly sits above the (average) water interface with a well dened radius which can be estimated from the gure as 1.75 nm. Using cos q = d/R, the data plotted in Fig. 4 predicts an average contact angle of 150. Although there are signicant uctuations of the contact angle on a timescale of tens of picoseconds, this average value is in excellent agreement with that estimated from the density plot taken from a subset of equilibrium congurations, Fig. 5. The particulate as a whole is partially dry in the water interface.

The surface pressure on the bar is measured at each area producing a curve similar to that shown in the Fig. 7. A standard analysis [1921] of the shape of the curve suggests that the size and contact angle made by the particle with the uid surface can be obtained from the curve. In particular the analysis suggests that the collapse pressure depends on the contact angle since it occurs when particles are ejected from the monolayer to form a bilayer. Hence we can measure nanoscale

3. Nanoparticulate arrays A popular method of characterising particulates is to use a LT to produce surface pressure (P) area (A) curves. Particulates are spread at the uid interface and conned to a given area by a moveable bar (Fig. 6(a)).
Fig. 5. Density prole of the passivated gold nanoparticle at equilibrium in the water interface at 298 K. The simulation contained a slab of saturated liquid water comprising 1000 , water molecules in a cell of dimension 60 60 100 A3. The , contour plot shows a half plane 25 100 A2 (one scale point , to 0.25 A). These preliminary data were averaged over 566 equilibrium congurations.

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Fig. 6. The LT experiment and the analogous simulation cell.

contact angles, (as well as line tensions) from this simple experiment. Such characterisations depend on the correct interpretation of the pressure area isotherm and it is this interpretation which we have investigated using molecular simulation. Fig. 6(b) illustrates the simulation method. We have a lm of liquid with two LV surfaces at one of which we place model spherical nanoparticles (here with diameter 8 times the diameter of the uid molecules). We consider particulates of two types as discussed in the previous section. In the rst case (Fig. 2(a)) there is a short range attrac-

Fig. 7. Pressure area curves from molecular dynamics of nanoparticles at LV interfaces.

tive particleuid molecule interaction and a short range repulsive particulateparticulate interaction. For this model we take 16 nanoparticles in 27 645 solvent particles with a contact angle with the liquid of 101. In the second case there is a LJs particulateuid molecule interaction and an attractive particulateparticulate interaction and we simulate 64 nanoparticles with a contact angle of 75 in a uid interface composed of 43 888 solvent particles. By changing the y and z dimensions of the simulation box (the system density remains constant) it is possible to measure surface pressures at different surface areas (from difference in the surface tension of the two interfaces) thus obtaining a pressurearea isotherm. The results of two simulations with particles having different contact angles are plotted in Fig. 7. The surface pressure has been normalised with respect to the surface tension of the LV interface. The simulation reproduces the typical shape of the experimental isotherms. The transition is marked by a knee in the curve beyond which the surface pressure is essentially constant. Note that the collapse pressure is equal to the interfacial surface tension of the pure interface. Indeed monolayers with different contact angles but in the same solvent collapse at the same pressure. In the standard interpretation based on particle promotion out of the interface at the knee, they should collapse at different pressures; the rst sign then that something is wrong with this view. Indeed by looking at computer graphics of the model particles in the interface as the area is reduced, a very different picture of what happens at the knee emerges. For the LJ/S nanoparticles (at T*= 0.5) with contact angle of 101, the LV interface containing the particulates, buckles [23], creating new area at a free energy cost which is lower than that required to promote a particle out of the interface. Such buckling has been seen experimentally for micron size particles [40]. For the LJs nanoparticles (at the higher temperature of T* =0.75) rather than buckle, the LV interface appears to roughen. Fig. 8(a) shows a snapshot of a monolayer of 64 nanoparticles in the vicinity of the knee. A layer of solvent particles surrounds the colloids, indicating that at the collapse pressure the colloids remain strongly sol-

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ticle MFP as a function of nanoparticle separation by considering a nanoparticle dimer at the LV interface. The results shown in Fig. 9 represent the contribution to the MFP, DF due to the solvent only (subtracting out the direct LJs interaction). The curve shows features typical of those observed in colloid depletion force plots, such as the maximum at |f, and the oscillations at larger distances. The force induced by the solvent is essentially negligible for separations larger than 4.5|f. At very short separations, DF remains positive and repulsive, reecting the preference of the nanoparticle to be solvated. Clearly in these conditions the collapse of the array under pressure involves solvated nanoparticles with an effective size larger than in vacuum. We expect a collapse surface area which is signicantly larger than the close packing area, as indeed observed in Fig. 7.

4. Summary From our studies of model LJs nanoparticles at LJs interfaces we conclude that it is possible to describe the wetting of nanoscale interfaces (down to 1 nm) using Youngs equation when (a) the uiduid interfacial tensions are large and (b) the three phase line has a small curvature. These general results have been obtained using idealised structureless model nanoparticulates. In nature however nanoparticles have internal and surface structures, are not necessarily rigid and the solvents may themselves be complex. Our preliminary results for passivated gold nanoparticles at water interfaces indicate that such particles have a well-dened mean contact angle with however signicant uctuations on a timescale of tens of picoseconds. Our simulations of nanoparticle arrays in the LT conguration strongly suggest that the collapse pressure measured in LT experiments is independent of contact angle and that such experiments cannot be used to determine contact angles. We expect the array to collapse by surface roughening when the surface pressure is equal to the surface tension of the pure solvent interface. In experiments where a different collapse pressure is observed we suggest that contamination of the

Fig. 8. (a) Snapshot of the nanoparticle array at the knee of the curve in Fig. 7 for a contact angle of 72; (b) nanoparticle solvent radial distribution function at the collapse pressure.

vated. This conclusion is reinforced by Fig. 8(b), which shows the solvent nanoparticle radial distribution function for this monolayer. As suggested by the snapshot there is a layer of solvent, which is strongly adsorbed at the nanoparticle surface. In addition we have analysed the mean force potential (MFP) of the colloids due to the solvent particles. We have calculated the nanopar-

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Fig. 9. Potential of mean force for solvated nanoparticles with a contact angle of 72.

uid interface by surfactant or other components of the system is likely to be responsible.

Acknowledgements We thank EPSRC for support through grant GR/M94427, GR/R39726.

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