A computational study of the surface structure and reactivity of

calcium fluoride

Nora H. de Leeuw*a,b and Timothy G. Cooperb,c

a
School of Crystallography, Birkbeck College, University of London, Malet Street, London,
UK WC1E 7HX. E-mail: n.deleeuw@mail.cryst.bbk.ac.uk
b
Department of Chemistry, University College, 20 Gordon Street, London, UK WC1H 0AJ
c
Department of Chemistry, University of Reading, Whiteknights, Reading, UK RG6 6AD

Received 15th August 2002, Accepted 2nd October 2002

First published as an Advance Article on the web 12th November 2002

Electronic structure calculations based on the density functional theory (DFT) are employed to investigate the
electronic structure of fluorite (CaF2) and the mode and energies of adsorption of water at the main {111}
cleavage plane. Electron density plots show the crystal to be strongly ionic with negligible ionic relaxation of
the unhydrated surface. We find associative adsorption of water at the surface with hydration energies between
41 and 53 kJ mol21, depending on coverage. We next employ atomistic simulation techniques to investigate the
competitive adsorption of water and methanoic acid at the planar and stepped {111}, {011} and {310}
surfaces. The hydration energies and geometries of adsorbed water molecules on the planar {111} surface agree
well with those found by the DFT calculations, validating the interatomic potential parameters. Methanoic acid
adsorbs in completely different configurations on the three surfaces, but always by one or both oxygen atoms
to one or more surface calcium atoms. Molecular Dynamics simulations at 300 K show that the effect of
temperature is to increase the difference in adsorption energy between methanoic acid and water at the planar
{111} surface. The methanoic acid remains bound to the surface whereas the water molecules prefer to form a
droplet of water between the two surface planes. We show in a series of calculations of the co-adsorption of
water and methanoic acid that the presence of solvent makes a significant contribution to the final adsorption
energies and that the explicit inclusion of solvent in the calculations is necessary to correctly predict relative
reactivities of different surface sites, a finding which is important in the modelling of mineral separation
processes such as flotation.

1 Introduction potential techniques to model larger scale systems. Comparison

Fluorite (CaF2) is a widely distributed mineral and it often
occurs in combination with a range of other ores, notably lead
and tin ores, and together with calcite and apatites.1 It is the
most important source material for hydrofluoric acid2 and as
such needs to be efficiently separated from any co-existing
minerals, usually by the technique of froth flotation, e.g. refs. 3
and 4. In addition to numerous investigations of the fluorite
structure itself, both experimental and computational, e.g.,
refs. 5–7 its crystal growth and dissolution have been widely
studied, e.g., refs. 8–10, as well as its possible application as a
substrate for the epitaxial growth of thin films.11 The effect of
hydration on the CaF2 surface structure is of considerable
interest in all of these applications, while the adsorption of
organic surfactant molecules at the surfaces is important in
mineral processing techniques, such as flotation, where the
selectivity of the surfactants plays a major rôle in the design of
a successful separation process.3,4
In this paper, we describe our computational investigations
of the electronic structure of the fluorite crystal and the sur-
face reactivity towards water and methanoic acid. We use
methanoic acid as a model of carboxylic acid surfactants such
as oleic acid, and study its adsorption at the major {111}, {011}
and {310} surfaces of calcium fluoride, including a series of
stepped surface sites. The approach we have chosen to adopt is
to use electronic structure calculations based on the density
functional theory (DFT) to study the main {111} cleavage
plane of fluorite in order to obtain, firstly, details of the
geometry and electronic structure of the dry and hydrated
surfaces, and secondly, reliable estimates of the hydration
energies to compare with when using classical interatomic
of the geometries and energies of adsorbed water molecules at
the calcium fluoride surface, obtained using both quantum
mechanical and classical techniques, will give an indication as
to whether the potential model used in the atomistic simu-
lations is capable of reliably modelling fluorite–water interac-
tions. If there is good agreement between the results of the
different methods, we can then be confident of applying ato-
mistic simulations to larger systems, including both adsorbing
species, which are currently beyond the capability of electronic
structure calculations.
2 Methodology
In the electronic structure calculations, the total energy and
structure of the simulation system, comprising slabs of solid
material separated by a vacuum gap, which together are
repeated periodically in three dimensions, was determined
using the Vienna Ab Initio Simulation Program (VASP).12–15
The basic concepts of density functional theory (DFT) and the
principles of applying DFT to pseudopotential plane-wave
calculations has been extensively reviewed elsewhere.16–18
Furthermore, this methodology is well established and has
been successfully applied to the study of adsorbed atoms and
molecules on the surface of ionic materials.19–22 The VASP
program employs ultra-soft pseudo-potentials,23,24 which
allows a smaller basis set for a given accuracy. Within the
pseudo-potential approach only the valence electrons are
treated explicitly and the pseudo-potential represents the
effective interaction of the valence electrons with the atomic
cores. In our calculations the core consisted of orbitals up to

DOI: 10.1039/b208004d J. Mater. Chem., 2003, 13, 93–101 93

This journal is # The Royal Society of Chemistry 2003
and including the 1s orbital for fluorine and oxygen and the 3p
orbital for Ca (H has no core). The valence orbitals are
represented by a plane-wave basis set, in which the energy of
the plane-waves is less than a given cutoff (Ecut).
For surface calculations, where two energies are compared, it
is important that the total energies are well converged. The
degree of convergence depends on a number of factors, two of
which are the plane-wave cutoff and the density of k-point
sampling within the Brillouin zone. We have by means of a
series of test calculations on bulk CaF2, where these parameters
were varied systematically, determined values for Ecut (500 eV)
and the size of the Monkhorst–Pack25 k-point mesh (3 6 3 6 3)
so that the total energy is converged to within 0.05 eV.
The electronic structure calculations were performed within
the generalized-gradient approximation (GGA), using the
exchange-correlation potential developed by Perdew and
Wang,26 which approach has been shown to give reliable
results for the energetics of adsorbates, e.g., water on CaO,27
TiO2 and SnO2.28
The larger scale systems were modelled using the less
computationally expensive atomistic simulation techniques,
based on the Born model of solids,29 where simple para-
meterised analytical forms are used to describe the forces
between atoms. In this work we employ the METADISE
code30 to investigate the surface systems by energy minimisa-
tion, which is achieved by adjusting the atoms in the system
until the net forces on each atom are zero. Energy minimisation
simulations will yield adsorption energies, which have pre-
viously been shown to give good agreement with experimental
surface sampling techniques such as temperature programmed
desorption, e.g., ref. 31, as well as lowest energy configurations
of the adsorbate/solid interface.
In addition, we employed Molecular Dynamics (MD)
simulations to derive the potential parameters for the water–
methanoic acid interactions and also to investigate whether the
inclusion of temperature in the calculations would affect the
adsorption behaviour and/or energies. The MD code used was
DL_POLY32 where the integration algorithms are based
around the Verlet leap-frog scheme.33 We used the Nosé–
Hoover algorithm for the thermostat,34,35 as this algorithm
generates trajectories in both NVT and NPT ensembles, thus
keeping our simulations consistent. The Nosé–Hoover para-
meters were set at 0.5 ps for both the thermostat and barostat
relaxation times. The surface simulations were run for at least
500 ps each (approximately 2.5 6 106 timesteps) as an NVT
ensemble, i.e., a constant number of particles, constant volume
and a constant temperature of 300 K.
We used a combination of three potential models for a
description of the interactions of the various atoms in the
systems, namely by Catlow et al., for the calcium fluoride
crystal;36 the cvff forcefield for methanoic acid;37 and the water
potential model by de Leeuw and Parker.38 The parameters for
the interactions between water and methanoic acid with the
fluoride surfaces were derived following the approach by
Schröder et al.,39 while the water–methanoic acid parameters
were fitted to the experimental solvation energy of methanoic
acid.40 The full potential model is given in Table 1.
3. Results and discussion
Calcium fluoride has the cubic fluorite crystal structure with
space group Fm3m and a ~ b ~ c ~ 5.4323 Å, where each
calcium ion is surrounded by eight fluoride ions, which are in
turn coordinated to four calcium ions in a tetrahedral
arrangement, shown in Fig. 1. The calcium ions are arranged
on a cubic face-centred lattice, and if we divide the unit cell into
8 smaller cubes, we find the fluoride ions in the centres of these
cubes.41 The cleavage plane is the {111} surface, which consists
of planes of calcium ions in a hexagonal array with a layer of
94 J. Mater. Chem., 2003, 13, 93–101
fluoride ions both above and below.9 The {111} surface is thus
terminated with fluorine atoms and just below the surface are
seven-coordinate calcium ions. We first employed DFT
methods to investigate the dehydrated {111} surface, calculat-
ing lattice parameters of a ~ b ~ c ~ 5.4051 Å, in excellent
agreement with experiment. Fig. 2 shows the relaxed {111}
surface, including the electron density distribution around the
calcium and fluoride ions and interatomic distances, from
which it is clear that the ionic relaxation of the surface is small,
a dilation of the topmost F–Ca spacing of 0.01 Å, followed by a
contraction of the second interlayer distance by 0.02 Å. The
contour plots of the electron density show that the crystal is
strongly ionic with electron density firmly centred on the
anions. The distortion of the electron density round the surface
ions is minimal, which leads to the negligible ionic relaxation of
the surface layer.
3.1 Hydrated {111} surface
We next investigated the adsorption of water at the {111}
surface to evaluate the energies of adsorption and the relaxed
hydrated surface structure. We studied both the adsorption of a
full monolayer (i.e. one water molecule per surface calcium ion)
and a 50% partial coverage. We used a range of different
starting configurations of associatively adsorbed water mole-
cules on the surface to ensure that the final converged
configuration would be a global, rather than a local, minimum
energy configuration. The hydration energy per water mole-
cule for the partial coverage of 50% was calculated to be
253.4 kJ mol21 compared to the sum of the energies for the
dry surface and an isolated gaseous water molecule, which
decreased to 241.4 kJ mol21 for full monolayer coverage.
These calculated hydration energies of approximately 41–
53 kJ mol21 suggest that the water molecules are physisorbed
rather than chemisorbed onto the surface. At 50% partial
coverage (Fig. 3), the water molecules adsorb almost flatly
onto the surface and are much more closely coordinated to
the surface than at full monolayer coverage; the calcium–
oxygen distance increases from 2.37 Å to 2.62 Å and the
fluorine–hydrogen distance from 1.52 Å to 1.67 Å when the
coverage is increased. This result suggests that the lattice
spacing of fluorine is not large enough to accommodate a full
layer of water molecules in an optimum position.
The DFT calculations did not show any dissociation of the
water molecules to form a hydroxylated surface at either
coverage, so in order to be certain that there was no lower
energy configuration with dissociatively adsorbed water
molecules, we also simulated a fully hydroxylated surface as
a starting configuration. A hydroxyl group was placed above
each surface calcium ion and a proton above each surface
fluoride ion. However, the dissociatively adsorbed water
molecules reassembled to form molecular water. Fig. 4 shows
the sequence of reformation of the water molecules on the
{111} surface, from initial configuration to a midway snapshot,
where tilting of the hydroxyl group towards the proton and
lengthening of the H–F bond (from 1.2 Å to 1.7 Å) is observed,
to the final configuration with associatively adsorbed water
molecules. The distance between the hydroxyl oxygen atom
and the proton decreases from an initial hydrogen-bond
distance of 2.22 Å to a normal O–H bond of 1.01 Å. The
calculated hydration energy of 241.3 kJ mol21 is identical to
the associative starting configuration (monolayer coverage),
giving us confidence that the lowest energy configuration had
been found. The easy reformation of undissociated water
molecules indicates that there is no significant energy barrier to
this process.
The preference for associatively rather than dissociatively
adsorbed water on the main CaF2 {111} surface agrees
qualitatively with previous atomistic and electronic structure
calculations of water adsorption at the vacuum interface of
Table 1 Potential parameters used in this work (short range cutoff 20 Å)

Charges (e)

Ion Core Shell Core-shell interaction/eV Å22

F 11.380 22.380 101.200000

Oxygen of carbonate group (O) 10.587 21.632 507.400000
Oxygen of water (Ow) 11.250 22.050 209.449602
Ca 12.000
Carbon of carbonate group (C) 11.135
Hydrogen of water (Hw) 10.400
Doubly-bonded oxygen of methanoic acid (OD) 20.380
Hydroxy oxygen of methanoic acid (OH) 20.380
Carbon of methanoic acid (CD) 10.310
Hydroxy hydrogen of methanoic acid (HO) 10.350
Hydrogen attached to carbon of methanoic acid (HC) 10.100
Buckingham potential
Ion pair A/eV r/Å C/eV Å6
Ca–O 1550.0 0.29700 0.0
Ca–F 1272.8 0.2997 0.0
Ca–Ow 1186.6 0.29700 0.0
Hw–O 396.3 0.23000 0.0
Hw–Ow 396.3 0.25000 10.0
O–O 16372.0 0.21300 3.47
F–F 99731833.99084 0.12013 17.02423
O–Ow 12533.6 0.21300 12.09
Ca–OH 563.64 0.29700 0.0
F–Ow 79785220.99 0.12013 26.78752
F–Hw 715.339 0.2500 10.00
Ca–OD 563.64 0.29700 0.0
OH–O 37898119 0.12013 11.309
OD–O 37898119 0.12013 11.309
OH–F 37898119 0.12013 25.1
OD–F 37898119 0.12013 25.1
Ow–OH 4797.6 0.213 30.2
Ow–OD 4797.6 0.213 30.2
Ow–HO 396.3 0.25 0.0
Ow–HC 396.3 0.25 0.0
Ow–CD 895 0.26 0.0
Lennard–Jones potential
A/eV Å12 B/eV Å6
Ow–Ow 39344.98 42.15
HC–O 2915.25 4.222
HO–O 2915.25 4.222
CD–O 3315.91 19.846
OD–Hw 1908.1 5.55
OH–Hw 1908.1 5.55
HC–F 2915.25 9.3784
HO–F 2915.25 9.3784
CD–F 3315.91 44.012
Morse potential
D/eV a/Å21 r0/Å
C–O 4.710000 3.80000 1.18000
Hw–Ow 6.203713 2.22003 0.92376
CD–HC 4.66 1.77 1.10
OH–HO 4.08 2.28 0.96
CD–OH 4.29 2.00 1.37
CD–OD 6.22 2.06 1.23
Three-body potential
k/eV rad22 H0̃
Ocore–C–Ocore 1.69000 120.000000
H–Owshell–H 4.19978 108.693195
OH–HO–CD 4.29 112.000000
CD–HC–OH 4.72 110.000000
CD–OD–HC 4.72 120.000000
CD–OD–OH 12.45 123.000000
Four-body potential
k/eV rad22 H0̃
C–Ocore–Ocore–Ocore 0.11290 180.0
Intermolecular Coulombic interaction (%)
Hw–Ow 50
Hw–Hw 50

MgO, another ionic crystal of cubic space group Fm3m, which and only occurs at defects and low-coordinated surface sites44–
46
showed that dissociative adsorption is energetically unfavour- or at the liquid water interface where H3O1 species are taken
able on the perfect {100} cleavage plane, e.g., refs. 19,31,42,43, into account.43 Electronic structure calculations of the main

J. Mater. Chem., 2003, 13, 93–101 95

 Fig. 3 Plan view of the minimum energy structure of the CaF2 {111}
surface with 50% coverage of associatively adsorbed water molecules,
showing almost flat adsorption of the water molecules (fluorite shown
as framework, water space-filled; Ca ~ black, F ~ pale grey, O ~
black, H ~ white).

Fig. 1 Bulk structure of CaF2 showing cubic face-centred calcium

lattice with the fluoride ions in the centres of each of eight smaller cubes
making up the cubic unit cell (Ca ~ black, F ~ pale grey).

Fig. 2 Side view of the relaxed CaF2 {111} surface showing electron
density contour plots and interatomic distances (Ca ~ dark grey, F ~
pale grey, contour levels are from 0.05 to 0.35 e Å23 at 0.05 e Å23
intervals, bond lengths in Å).

TiO2 cleavage plane, the {110} surface, show hydroxylation of

the surface at half coverage.20,28 However, Lindan et al. found
that at full coverage a mixture of associatively and dissocia-
tively adsorbed water molecules is observed, where the water
molecule is adsorbed almost flat onto the surface to maximise
hydrogen-bonding to oxygen atoms of both the hydroxyl group
and the mineral surface.20 This configuration of the associa-
tively adsorbed water molecules on the TiO2 {110} surface is
thus like that on the CaF2 {111} surface, where almost flat
Fig. 4 Reassembly of dissociatively adsorbed water molecules on the
CaF2 {111} surface: (a) side view showing initial configuration of
hydroxylated surface; (b) snapshot during minimisation process
showing tilting of hydroxyl group and lengthening of F–H bond; (c)
side view of the final configuration showing associatively adsorbed
water molecules (crystal shown as framework, water space-filled; Ca ~
black, F ~ pale grey, O ~ black, H ~ white).

96 J. Mater. Chem., 2003, 13, 93–101

adsorption of the water molecules and a network of hydrogen- with close coordination of both hydrogens to surface fluoride
bonding is preferred over dissociative adsorption. ions, while the water molecules in the DFT calculations adsorb
Our calculations indicate that the binding of the water slightly tilted, with one hydrogen atom pointing away from the
molecule’s oxygen atom to a surface calcium atom is the main surface, giving very different H–F distances for the two hydro-
interaction. This finding suggests that increasing the coordina- gens (1.52 Å and 2.85 Å). When a full monolayer is adsorbed,
tion of the surface cation to the bulk value, from seven- to the average adsorption energy drops to 38.5 kJ mol21,
eight-coordinate for the {111} surface, is the driving force compared to 41.4 kJ mol21 for the DFT calculations. Due to
behind the adsorption. From these calculations we would lack of space on the surface for a full monolayer, the water
therefore suggest that, as with MgO, dissociative adsorption of molecules do not adsorb flat onto the surface and the lesser
water takes place at defects and low-coordinated surface sites binding between surface fluoride ions and hydrogen atoms
rather than the higher-coordinated cations of the perfect {111} leads to an even better agreement for the adsorption energies
cleavage plane. between the two computational techniques. On the {011} and
{310} surfaces, the Ca–Ca spacings are large enough easily to
accommodate a full monolayer of water. On the {011} surface,
3.2 Hydration of planar and stepped surfaces
the water molecules adsorb in an upright fashion, without
In order to study larger-scale systems, we employed atomistic significant H–F interactions. However, the increased stability
simulation techniques to model two more fluorite surfaces in of the hydrated {310} surface is due to flat adsorption of the
addition to the {111} surface, namely the {011} and {310} water molecules, similar to the {111} surface, and an extensive
surfaces, as well as two stepped {111} surfaces, as a more network of hydrogen-bonding between both hydrogens and
realistic model for experimental surfaces. We investigated surface fluoride ions.
adsorption of both water and methanoic acid on the surfaces to As ‘real’ surfaces are never completely free from defects, we
evaluate their relative structures and adsorption energies. have also included stepped surface sites in our calculations. We
We first modelled the unhydrated surfaces to calculate their considered two steps on the {111} surface that differ in the
stabilities, after which we hydrated the surfaces to evaluate any orientation of the F2 groups, which either lean backwards at an
changes in stability. The surface stabilities are measured by the obtuse angle of 135u with respect to the underlying plane or
surface energy, which is calculated as follows: forwards at an acute angle of 45u (Fig. 5). From the adsorption
energies in Table 3, we see that hydration of the acute step edge
Us {Ub is less favourable than the planar surface, due to the restricted
c~
A space available for the adsorbing water molecule under the
step. However, the more open adsorption site at the obtuse step
where Us is the energy of the ions in the surface simulation cell edge, combined with the step ions’ lower coordination number,
and Ub is the energy of an equal number of bulk ions, while A is makes hydration of this step more exothermic than the planar
the area of the surface. A low, positive value for the surface surface.
energy indicates a stable surface, which will be important in the
morphology of the mineral. The surface energies of the dry and
hydrated surfaces are collected in Table 2, where the surface 3.3 Adsorption of methanoic acid
energy of the hydrated surface is calculated with respect to bulk
water. The {111} surface is clearly the most stable of the three When we considered adsorption of methanoic acid at the same
surfaces considered, both in dry and aqueous conditions, in surface sites, we found that the methanoic acid molecules
agreement with the fact that this is experimentally the perfect adsorb onto the planar surfaces in three distinctly different
cleavage plane of calcium fluoride.41 The dry {310} surface is
very unstable, but its stability is increased substantially when
the surface is hydrated, making it now more stable than the
{011} surface.
We first considered adsorption of water on the planar {111}
surface, where comparison to the equivalent DFT calculations
gives an indication of the accuracy of the potential model. The
water molecules adsorb flat onto the surface at a Ca–O distance
of 2.47 Å and H–F distances of 2.13–2.18 Å. As suggested by
the DFT calculations, the Ca–Ca interatomic spacing of 3.85 Å
is too small for a water molecule to adsorb on each calcium ion,
and hence only 50% of the available adsorption sites are
covered by water molecules. We again calculated the adsorp-
tion energies with respect to isolated gaseous water molecules
to enable direct comparison with experimental techniques such
as temperature programmed desorption (TPD). We calculated
a hydration energy of 261.8 kJ mol21 at a partial coverage of
50%, which is in acceptable agreement with the DFT result of
253.4 kJ mol21. The discrepancy in the hydration energies is
due to the fact that the atomistic simulations predict a
completely flat mode of adsorption for the water molecules,

Table 2 Surface energies of the calcium fluoride surfaces

Surface energies/J m22

Surface Unhydrated Hydrated

{111} 0.52 0.40

{011} 0.82 0.90
Fig. 5 (a) Acute and (b) obtuse steps on the CaF2 {111} surface (Ca ~
{310} 1.56 0.67
black, F ~ pale grey).

J. Mater. Chem., 2003, 13, 93–101 97

Table 3 Adsorption energies of water and methanoic acid at the
surfaces

Adsorption energies/kJ mol21

Methanoic acid
Surface Water Methanoic acid in water

Planar {111} 238.5 256.3 296.7

Acute {111} 229.1 290.8 234.1
Obtuse {111} 250.8 279.5 221.2
{011} 233.4 2102.4 —
{310} 2250.7 2110.9 —

fashions. On the {011} surface, the lattice spacing is large

enough to allow full monolayer coverage with one methanoic
acid molecule per surface calcium. The methanoic acid
molecule adsorbs with both oxygen ions to two surface calcium
ions, bridging between them (Fig. 6). The doubly bonded
oxygen ion closely coordinates to the calcium ion at a distance
of 2.2 Å while the oxygen atom of the hydroxyl group is at
2.65 Å from the second calcium ion. The hydrogen of the
hydroxyl group relaxes into the surface and coordinates to a
fluorine atom at 2.4 Å. The lattice spacing on the {310} surface
is also large enough to accommodate full monolayer coverage
(Fig. 7). The doubly bonded oxygen ion is again bonded to a
surface calcium ion at 2.15 Å, while more loosely coordinated
Fig. 6 Side view of the {011} surface, showing the crystal as a lattice
framework (Ca ~ black, F ~ pale grey) and the methanoic acid
molecule (space-filled, O ~ black, C ~ pale grey, H ~ white)
coordinated by its oxygens to two surface calcium ions.
Fig. 8 Plan view of the {111} surface with adsorbed methanoic acid
molecule, showing the crystal as a lattice framework (Ca ~ black, F ~
pale grey) and the methanoic acid molecule (space-filled O ~ black,
C ~ pale grey, H ~ white).
to calcium ions further away in the next layer (3.93 Å).
Furthermore, the doubly bonded oxygen ions coordinate to
hydroxyl hydrogens of other adsorbed methanoic acid
molecules (2.4 Å), while the hydrogen bonded to the carbon
atoms coordinates to surface fluoride ions (2.35 Å).
Due to the much smaller interatomic distance on the {111}
surface, only a 50% coverage of methanoic acid can be
accommodated, which is a reasonable coverage if we compare
it with experimental work by Mielczarski et al., who observed a
30% coverage of oleic acid, which is a carboxylic acid with a
long carbon chain instead of the hydrogen of methanoic acid.47
The molecules adsorb in a fairly flat configuration onto the
surface, bridging between two calcium ions, with both oxygen
ions coordinated to a calcium at 2.2 Å for the doubly bonded
oxygen ion and at 2.9 Å for the oxygen ion of the hydroxyl
group (Fig. 8). The hydrogen atom of the hydroxyl group
coordinates to two surface fluoride ions at 2.5 and 2.7 Å. When
adsorbed at the step edges, we see that the trend in adsorption
energies is reversed from the hydration pattern. More energy is
now released upon adsorption at the acute step edge than at the
obtuse edge, while both steps are calculated to be more
favourable adsorption sites than the terraces of the planar
surface. The reason for the higher exothermicity at the acute
step edge is the fact that in addition to the same interactions
between methanoic acid and the terrace atoms, as shown for
adsorption on the planar surface, the doubly bonded oxygen
atom also bonds to a low-coordinated calcium ion on the step
edge, hence bridging the gap between step and terrace, which
was not possible in the adsorption of water. The hydrogens also
interact with fluoride ions both on the edge and the terrace,
leading to a network of hydrogen-bonding between the surface
and adsorbate. It is these multiple interactions that cause the
methanoic acid adsorption at the steps to be more exothermic
than on the planar surfaces.

3.4 The effect of temperature: Molecular Dynamics simulations

Fig. 7 Side view of the {310} surface, showing the crystal as a lattice
framework (Ca ~ black, F ~ pale grey) and the methanoic acid
molecule (space-filled, O ~ black, C ~ pale grey, H ~ white) closely
coordinated by its doubly bonded oxygen atom to a surface calcium ion
and hydrogen-bonding to a surface fluorine.
of the (111) surface
As energy minimisation techniques do not take into account
temperature, in this section we employ Molecular Dynamics
simulations (MD) to explicitly investigate the effect of tempera-
ture on the interaction of water and methanoic acid at the
{111} plane at 300 K. We started the simulations with a
monolayer of water adsorbed at the surface. However, during
the simulation water molecules desorbed from the surface and
diffused through the gap between the two surfaces, forming
a droplet (Fig. 9). From the mean square deviation, the
diffusion coefficient of the water molecules is calculated to be

98 J. Mater. Chem., 2003, 13, 93–101


Fig. 9 Water droplet formation between two {111} surfaces in a
Molecular Dynamics simulation at NVT and 300 K.
1.2 6 1029 m2 s21, which is identical to that calculated for
water molecules in a box of pure liquid water at 300 K under
NPT conditions.38 The hydration energy of 232.7 kJ mol21 at
300 K is less than the intermolecular interactions between
water molecules themselves, calculated to be 243.0 kJ mol21
at the same temperature in agreement with experiment
(243.4 kJ mol21).48 Hence, at this low water density, we
may conclude that on energetic grounds the water molecules on
the fluorite {111} plane prefer not to adsorb to the surface but
to cluster together. We next repeated the calculation with
methanoic acid as the adsorbate rather than water. This time,
however, the methanoic acid remained bound to the {111}
surface rather than diffuse through the gap. Clustering of the
methanoic acid molecules also took place, but unlike the
water molecules, surface diffusion of the methanoic acid was
followed by the formation of clusters at the surface, in a similar
adsorption pattern as was observed in the energy minimi-
sation calculations above, by both oxygen atoms to surface
calcium ions (Fig. 10). Similar clustering of methanoic acid was
observed experimentally by Iwasawa et al. to occur at terraces
on the TiO2 (110) surface.49 The energy of interaction of
methanoic acid with the surface is calculated at 291 kJ mol21,
higher than in the energy minimisation simulations. Hence, the
Fig. 10 Adsorption and clustering of methanoic acid molecules at the
{111} surface in a Molecular Dynamics simulation at NVT and 300 K.
effect of temperature, included in calculations through the
employment of Molecular Dynamics simulations, is to exacer-
bate the difference in adsorption energies between water and
methanoic acid at the fluorite (111) surface. The MD simu-
lations also showed that although the methanoic acid diffuses
along the surface, it remains adsorbed, while competitive
interactions between the water molecules themselves outweigh
interactions between the solid surface and water molecules,
which as a result leave the surface.
Of course, in ‘‘real’’ mineral separation processes, water
and the organic flotation reagents co-exist and we have hence
extended our calculations to include both water and methanoic
acid in the simulations.
3.5 Co-adsorption of water and methanoic acid
The adsorption energies from the energy minimisations for
both water and methanoic acid onto the three surfaces are
collected in Table 3. The hydration energies for the different
calcium fluoride surfaces vary considerably due to the presence
(or absence) of hydrogen-bonding to the surface fluoride ions,
in addition to the calcium–oxygen interactions. The adsorption
energies for methanoic acid onto the mineral surfaces are
considerably larger than the hydration energies on the domi-
nant {011} and planar and stepped {111} surfaces due to the
capability of the acid molecules to bridge, by their oxygen
atoms, between two or more surface calcium atoms and the
close hydrogen-bonding to surface fluoride ions. These calcu-
lations would therefore suggest that it would be energetically
preferential for the methanoic acid molecules to adsorb to these
surfaces, displacing the water molecules from the adsorption
sites, which was borne out by the MD simulations of water and
methanoic acid at the {111} surface at 300 K, where the water
desorbed from the surface while the methanoic acid remained
adsorbed. However, in order to verify whether this assumption
based on separate calculations of the adsorbates is valid, we
repeated the calculations of methanoic acid adsorption at the
planar and stepped {111} surfaces, but this time including a
layer of water in the simulations, hence studying the compe-
titive adsorption of water and methanoic acid directly. The
adsorption energies were now calculated with respect to the
hydrated surface and a solvated methanoic acid molecule. In
order to model the co-adsorption of methanoic acid and water
at the fluorite surfaces, we needed to derive interatomic
potential parameters for the water–methanoic acid interac-
tions. We fitted these potential parameters to the experimental
solvation energy of methanoic acid, in a series of Molecular
Dynamics simulations of a methanoic acid molecule in a box of
255 water molecules (Fig. 11). The final parameters thus
derived (Table 1) gave a solvation energy for methanoic acid
of 241.7 kJ mol21, compared to the experimental value of
247.4 kJ mol21.40
The data listed in Table 3 show that on the planar {111}
surface, the presence of water increases the adsorption energy
of methanoic acid, the reason for which becomes clear if
we compare the adsorption pattern of the methanoic acid
with that of water at the same surface sites. The methanoic acid
only replaces one adsorbed water molecule at the planar
surface and as the intermolecular interactions between the
water molecules themselves (43 kJ mol21) or with the
methanoic acid (40 kJ mol21) are very similar, the water
molecules have no preference for interacting with either the
methanoic acid or each other. The regular adsorption pattern
of the water on the surface is not disturbed by the presence of
the surfactant, but the adsorbate is stabilised by the forma-
tion of a network of hydrogen-bonded interactions to neigh-
bouring water molecules. However, at the stepped surface sites
the co-adsorption of water lowers the adsorption energies for
methanoic acid (Table 3), both processes becoming much less
exothermic. Again, the reason is two-fold, based on both the
J. Mater. Chem., 2003, 13, 93–101 99

Fig. 11 Average configuration of methanoic acid molecule in a
simulation cell of 255 water molecules during a Molecular Dynamics
simulation at NPT and 300 K (the apparently dissociated water
molecules are, in fact, water molecules, but shown split up as an artefact
of the periodic boundary conditions).
geometry of the surface sites and the relative adsorption
energies of the surfactant and the water molecules. Hydration
of the stepped sites (29–51 kJ mol21) is energetically similar to
the planar fluorite surface (average y38.5 kJ mol21). Binding
of the methanoic acid to the steps is stronger than water
(average y85 kJ mol21) and it therefore remains closely bound
to the step site even in the presence of water, as shown in
Fig. 12 for the obtuse step. However, its presence at the step
disturbs the regular pattern of water adsorption, at least in the
immediate vicinity of the step, leading to a smaller adsorption
energy. Thus, before the addition of water to the system we find
similar adsorption energies for the three different surface sites
on the {111} surface (56–91 kJ mol21), but once water has been
introduced in the calculations, the adsorption energies show a
much bigger variation with adsorption site (21–97 kJ mol21)
and even a reversal of the relative stabilities, indicating that we
need to include solvent effects explicitly if we are to predict
realistic adsorption behaviour.
4 Conclusions
We have shown in this work that computational techniques are
well placed to provide insight at the atomic level into the
interactions between substrate and adsorbate molecules. We
Fig. 12 Co-adsorption of water and methanoic acid at the obtuse step
on the {111} surface (fluorite as framework, methanoic acid space-
filled, water as triangles; Ca ~ dark grey, F ~ pale grey, O ~ black,
C ~ grey, H ~ white).
100 J. Mater. Chem., 2003, 13, 93–101
have presented calculations of the adsorption of water and
methanoic acid at calcium fluoride surfaces, using a combina-
tion of computational techniques. Accurate density functional
theory calculations were used to obtain the electronic struc-
ture of the {111} surface together with hydration modes
and energies; and atomistic simulation techniques to elucidate
the geometry and relative adsorption energies of water and
methanoic acid at a range of different surface sites. From our
simulations we can draw the following conclusions.
Electron density plots generated by DFT calculations of the
{111} surface show calcium fluoride to be a strongly ionic
crystal, with no discernible distortion in the surface layer with
respect to bulk layers, leading to minimal ionic relaxation of
the surface.
Associative adsorption of water is preferred at the {111}
surface, without significant energy barrier to reformation of
dissociated water molecules into molecular water. The hydra-
tion energy is dependent upon coverage and both the decrease
in hydration energy and lesser coordination to the surface upon
increasing coverage indicates repulsive interactions between the
adsorbed water molecules.
Modelling hydration of the {111} surface using atomistic
simulation techniques gives similar hydration energies and
configurations of the adsorbed water molecules to the DFT
calculations, although there may be some overbonding of the
H–F hydrogen-bonding in the interatomic potential approach.
Adsorption of methanoic acid up to full monolayer coverage
is possible on both {011} and {310} surfaces, but on the {111}
surface, due to the smaller calcium–calcium distance, only
adsorption up to 50% is preferred. On this surface, the
methanoic acid molecules adsorb by their oxygen atoms to two
calcium atoms, forming a bridge between them. This mode of
adsorption is particularly favourable, which is also seen at the
stepped sites on the {111} surface. On both the {011} and the
dominant {111} fluorite surfaces the energies of adsorption of
methanoic acid compared to water show that adsorption of
methanoic acid is energetically more favourable and hence
methanoic acid should compete effectively with water for
adsorption at these surfaces. Molecular Dynamics simulations
of the two adsorbates at the {111} surface show that the
effect of temperature is to widen the gap in adsorption energies
between methanoic acid and water. The latter adsorbate leaves
the surface and forms a water droplet between the {111}
planes.
Simulations of methanoic acid adsorption in the presence of
water bear out the suggestion that methanoic acid competes
effectively with water as an adsorbate, as the methanoic acid
remains adsorbed at the {111} terrace and steps forming close
interactions with the surrounding water molecules. However,
these latter calculations have also shown that interactions
between surfactant and water molecules can have a radical
effect on adsorption behaviour, and it is therefore not suffi-
cient to calculate the interactions of surfactant molecules with
mineral surfaces in isolation, as the presence of solvent in the
calculations makes a significant contribution to the final
adsorption energies and relative stabilities of the surface sites.
The implication of these findings for the search for flotation
reagents is that we need to explicitly include solvent in the
calculations if we are to successfully predict the affinity of the
mineral for particular surfactants.
Acknowledgements
We acknowledge the Engineering and Physical Sciences
Research Council, grant no. GR/N65172/01, and the Royal
Society, grant no. 22292, for funding and the Minerals and
Materials Consortia for the provision of computer time on the
Cray T3E.
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