Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

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Journal of Molecular Structure: THEOCHEM

journal homepage: www.elsevier.com/locate/theochem

Dehydration of goethite to hematite from molecular dynamics simulation

Wen-Juan Zhang a, Chun-Fang Huo a, Gang Feng a, Yong-Wang Li a, Jianguo Wang a, Haijun Jiao a,b,*
a
b

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China
Leibniz-Institut fr Katalyse e.V. an der Universitt Rostock, Albert-Einstein Strasse 29a, 18059 Rostock, Germany

a r t i c l e

i n f o

Article history:
Received 25 January 2010
Received in revised form 11 March 2010
Accepted 12 March 2010
Available online 17 March 2010
Keywords:
DFT calculation
Molecular dynamics
Goethite
Dehydration

a b s t r a c t
In FischerTropsch synthesis (FTS), the prepared catalyst hematite (a-Fe2O3) originates from goethite (aFeOOH) dehydration in calcinations process. The structure of a-FeOOH and its topotactic transformation
into a-Fe2O3 under 300900 K have been modeled within the framework of density functional theory.
Molecular dynamics simulations show that the transformation begins preferentially on the surface and
the dehydration is associated with the formation of voids. The loss of H2O in a-FeOOH does not modify
the morphology extremely with respect to that of the original a-FeOOH. The transformation process
involves hydrogen migration with the formation of adsorbed water, followed by desorption of the water
molecule. The calculated barriers for hydrogen migration (118 kJ/mol) and water desorption (82 kJ/mol)
suggest a direct reaction path without the formation of intermediates.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Iron oxides have attracted enormous attention owing to their
interesting electronic, magnetic, catalytic properties, chemical stability and relatively low production costs [14]. They have a wide
range of potential applications as electro-optic materials, sorbents,
pigments, ion exchangers, magnetic resonance imaging and particularly catalysts [510]. Hematite (a-Fe2O3) is thermodynamically
the most stable form of iron oxides under atmospheric conditions
and often the end form of oxidative transformation of other iron
oxides [11].
In FischerTropsch synthesis (FTS), iron oxide-based catalysts
are widely used due to their high watergas shift (CO + H2O = CO2 + H2) activity when coal-derived syngas is used as feeding
[12]. The prepared catalyst is a mixture mainly containing aFe2O3 and magnetite (Fe3O4).
It is known that a-Fe2O3 phase in iron catalysts originates from
goethite (a-FeOOH) dehydration in calcinations process [13,14],
and it is of scientic and technological importance for its detailed
dehydration process, which has been the subject of many studies
[1521]. XRD and Mssbauer studies revealed that the iron
oxide-based catalysts samples consist of a-FeOOH, Fe3O4 and aFe2O3 after precipitation, and there is no signicant phase transformation during the drying process at about 523 K [22]. Then with
temperature rising, a-FeOOH can transform to a-Fe2O3, which
has been proved to contribute signicantly to the catalyst surface

* Corresponding author at: State Key Laboratory of Coal Conversion, Institute of

Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China.
E-mail address: haijun.jiao@catalysis.de (H. Jiao).
0166-1280/$ - see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2010.03.013

area and pore volume [23]. However, the detailed mechanism of

the transformation from a-FeOOH to a-Fe2O3 is still unknown.
Experimental observations showed that each a-FeOOH unit cell
contains four (FeOOH) units [24,25]. Oxygen atoms are hexagonal
close-packed with the formation of octahedral interstices in which
ferric iron ions are located, and hydroxyls form zig-zag chains between the oxygen planes [2630]. Experimental studies suggested
that the thermally induced topotactic transformation of a-FeOOH
dehydration process can be either directly from a-FeOOH to aFe2O3 (2a-FeOOH ? a-Fe2O3 + H2O) [1519] or via a super structure intermediate named proto-hematite (or hydrohematite) to
form hematite (2a-FeOOH ? superstructure ? a-Fe2O3 + H2O)
[20,21]. Goss studied the kinetics of a-FeOOH dehydration and
proposed a direct transformation from a-FeOOH to a-Fe2O3 without the formation of an intermediate phase [15]. He found that
one of either proton or iron transfers across the reaction interface
with the formation of a porous reaction product at early stages and
at lower temperatures (below 513 K). Watari et al. observed the
presence of twins and two types of one-dimensional fringes because of the textural effects rather than the existence of a superstructure using high-resolution transmission electron microscopy
in the dehydration investigations [16,31]. In addition, they proposed that the reaction occurs preferentially at the surface of aFeOOH and with the dehydration proceeding, the formation of
voids can be easily observed [17,31]. Walter et al. and Cudennec
et al. were also of the opinion that it is a direct transformation from
a-FeOOH to a-Fe2O3 without the formation of intermediate
[18,19]. Walter et al. suggested that for a small-size a-FeOOH particle sample, the transformation temperature is around 543 K [18].
Cudennec et al. reported that a-FeOOH dehydrates in the temperature range of 533593 K [19]. However, zdemir et al. reported

W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

that in the temperature range of 511675 K, a-FeOOH dehydrated

partially with the formation of an intermediate phase [20]; and Wolska et al. showed that a hydrohematite [Fe1.83(OH)0.5O2.5] phase
formed during the thermal dehydration process of a-FeOOH [21].
Previous theoretical studies on a-FeOOH mainly paid attention
to the a-FeOOH surface and a-FeOOHH2O interfaces [3234]; and
no theoretical studies on a-FeOOH dehydration have been reported. The aim of our work is to investigate the mechanism of
thermal dehydration of a-FeOOH to a-Fe2O3, and provide a theoretical basis for experimental research.

2. Computational methods
All calculations were performed in the framework density functional theory (DFT) in the standard KohnSham formalism [35], as
implemented in Vienna ab Initio Simulation Package (VASP)
[36,37]. Atomic cores are described with the projected augmented
wave method (PAW) [38,39], used in combination with the Perdew, Burke and Ernzerhof exchangecorrelation functional (PBE)
[40]. The wave functions are developed on a basis set of plane
waves. Periodic boundary conditions are set. All these methods
were tested and validated [4144].
Fe-bearing minerals present a signicant challenge for calculations because of their magnetic properties [45]. In our study, we
must set the spin states of individual Fe atoms carefully because
a-FeOOH is anti-ferromagnetic [45]. The total energies of periodic
blocks of atoms are calculated within the generalized gradient
approximation (GGA) along with special treatment of on-site Coulomb interactions for d electrons on Fe, using the so-called GGA+U
approximation [4648]. In our study, the effective on-site Coulomb
and exchange interaction parameters for each Fe atom were set to
4 and 1 eV [45], respectively, and this was used for all Fe throughout the calculations. The magnetizations for the Fe atoms were set
to ve, with alternating in positive and negative spin directions to
make sure that the total magnetization of a-FeOOH is zero [49].
The cutoff energy is 700 and 500 eV for optimization and molecular
dynamics (MD) simulations, respectively, which ensures a good
convergence of the total energies.
The Monkhorst Pack scheme was used to generate the k-point
sampling grids within the Brillouin zone. The accurate precision level was used in the optimization of a-FeOOH bulk structure, while
for MD simulations low precision level is denitely sufcient. MD
simulations were performed in a canonical ensemble, using scaled
velocities to the temperature at each time step. The convergence
criteria for geometry optimization were set to: (a) SCF tolerance
of 1  10 4 eV, (b) atomic force tolerance of 0.02 eV/.
The nudged elastic band (NEB) method [5052] with eight
equally spaced images along the pathway is used to locate the minimum energy path and the transition state for the hydrogen migration from one hydroxyl group to the adjacent one without
considering quantum mechanical tunneling for the H-atom transfer. The vibrational frequency of H migration is determined by
diagonalizing a nite difference construction of the Hessian matrix
with displacements of 0.015 (only allowing relevant H and O
atoms to move). Energy difference of 1  10 6 eV was used as convergence criteria in the frequency calculation. Only one imaginary
frequency for the transition state structure was found, based on
which we can make sure that the transition state structure and
the activation energy calculated for the transition states is correct
and reliable. The computed activation barriers agree reasonably
with the available experimental data [5355].
Recently, Krokidis et al. studied the dehydration process of
boehmite (c-AlOOH) to c-alumina (c-Al2O3) by MD simulations
[56]. The elementary steps of c-AlOOH dehydration process have
been proposed and the proposed c-Al2O3 structure terminated

21

the long dispute on c-Al2O3 [5759]. Their results show that MD

method is a reliable choice to solve such dehydration process.
Thus, it is a good choice to investigate the similar dehydration process of a-FeOOH with MD simulations.
3. Results and discussion
3.1. Bulk a-FeOOH and a-Fe2O3

a-FeOOH has a double-chain structure, and hydrogen bonds form

zig-zag chain between the two chains. The bulk structure of a-FeOOH has been studied extensively with X-ray diffraction and neutron
diffraction [45,60,61]. The three-dimensional structure is built up
with FeO3(OH)3 octahedrons in which iron ions are located [19]. Besides, the structure of a-FeOOH can be described as a slightly distorted hexagonally close packed stacking of anions (O2 and OH )
which form large tunnels, spreading out along (0 1 0) direction in
which hydrogen atoms are located [19] as shown in Fig. 1a.
Our results show that the optimized parameters (a = 9.95 ;
b = 3.00 ; c = 4.60 ) for the bulk phase are in rather good agreement with the experimental results (a = 9.95 ; b = 3.01 ;
c = 4.62 ). The computed structural parameters (a = b = 5.035 ;
c = 13.720 ) of a-Fe2O3 also agree well with the previous investigations (a = b = 5.035/5.050 ; c = 13.747/13.770 ) [62,63]. These results suggest that the structure predicted by the methodology
described above is so reliable that we can use the similar computational approach to perform MD simulations of a-FeOOH dehydration
process.
As a-FeOOH, a-Fe2O3 can also be described as a slightly distorted hexagonally closed packed staking of anions (O2 ) with
the formation of the octahedral sites in which iron ions are located
(Fig. 1b) [19]. In a-FeOOH and a-Fe2O3, anion layers are stacked
perpendicularly to the c-axis which corresponds to the ABA stacking and can be easily observed from (Fig. 1c and d). Besides, the
distance of a-Fe2O3 layers is three times of a-FeOOH layers which
due to periodic shifts of cations (Fig. 1c and d) [19,21]. The structures of a-FeOOH and a-Fe2O3 appear similar, as a result of which
the transformation from a-FeOOH to a-Fe2O3 is topotactic which
can only exist between solids showing similar structures.
3.2. MD simulation
In a preliminary study, MD simulation of the heating process
has been performed on a periodic supercell composed with three
a-FeOOH primitive cells containing 12 Fe, 24 O and 12 H atoms
representing six a-FeOOH layers (Fig. 2). In addition, vacuum layer
was set to 10 along the large tunnels in the (0 1 0) direction to
avoid electronic coupling between the adjacent slabs and facilitates water departure. This was validated by Walter et al. [18]
and they thought that the diffusion distance for the water molecules to leave the a-FeOOH needle along the c-axis is too large.
In addition, building vacuum slab along the (0 1 0) direction is in
favor of the departure of the formed water. The system allows
relaxation and possible reconstruction along the (0 1 0) direction.
A heat bath from 300 K up to 900 K with a heating rate of 0.5 K/
fs (a time interval of 1.2 fs) has been used according to [56]. This
heating rate is reasonable since the morphology of the particles
after losing water molecules does not change signicantly with
respect to that of the original a-FeOOH [18,64]. The MD results
performed on a slab model representing the (0 1 0) surface of
a-FeOOH in Fig. 2 in the interval of 300900 K is shown in Fig. 3
(the same labels as in Fig. 2). Since the calcination temperature
of FTS catalyst preparation is about 500700 K, our choice of
300900 K is reasonable. During this simulation, hydrogen transfers between the adjacent hydroxyl groups have been observed.

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W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

Fig. 1. Top (a and b) and side (c and d) views of a-FeOOH and a-Fe2O3 (blue ball for Fe atom; red ball for O atom; and small white ball for H atom), respectively. (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 2. Schematic representation of the a-FeOOH periodic supercell used in MD simulation: (a) side view (b) top views. The arrows show the hydrogen transfers discussed in
the text and depicted in Fig. 3.

By considering the time-evolution of distance dened between

iron atoms Fe1 and Fe2 bonding to adjacent hydroxyl groups depicted by Fig. 3a, we found that Fe1 and Fe2 vibrate only near
the equilibrium position, and there is no obvious change of their
distance indicating that there is no new bond formation.
Fig. 3b shows that Fe1Fe3 distance shortens gradually as the
temperature hoisted, indicating the formation of Fe1Fe3 bond at
375 K; its normal band length is about 2.881 in a-Fe2O3. At
452 K, they begin to bond and nally bond to each other at

495 K. As temperature rises, Fe1 and Fe3 just vibrate near the equilibrium positions indicating the formation of a stable bond.
Fig. 3c shows that the Fe1O2 distance does not change so
much (about 2.0 ) at the initial temperature, indicating that they
just vibrate around themselves, but it gradually grows longer and
the bond cleaves as the temperature hoisted to about 600 K.
Fig. 3d shows that the Fe2O2 distance does not change (2.1 )
so much at initial temperature, indicating that they just vibrate
around themselves, but grows gradually longer as the temperature

W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

23

Fig. 3. MD results about the distance between atoms performed on a slab representing the (0 1 0) surface of a-FeOOH in the interval of 300900 K (red line represent the
distance between relevant two atoms in a-FeOOH). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

hoisted, nally resulting in bond cleavage at about 425 K, which

may also happen in the interval of 425507 K and 538645 K. With
the temperature rising up to 736 K, the Fe2O2 distance becomes
larger. From Fig. 3c and d, we can see that the temperature at
which Fe1O2 and Fe2O2 bonds cleave is also the temperature
for water formation.
Fig. 3e shows that the O2 transfers to Fe4 and nally bond to
each other at 720 K. The Fe4O2 distance is very short and changes
a little at higher temperature, indicating that they just vibrate
around themselves.
Fig. 3f shows that the H1O1 distance elongates as the temperature rising, and H1 O1 nally breaks at about 552 K.
Fig. 3g shows that the H1O2 distance shortens gradually as the
temperature hoisted, indicating that there will be temporary formation of H1O2 bond at about 560 K, then H1 and O2 will eventually bond to each other at 620 K and they just vibrate near their
equilibrium positions in the interval of 620655 K. The H1O2 distance elongates above 655 K, resulting nally in bond cleavage. The
temperature of water formation and dehydration interval have
been concluded from Fig. 3f and g.
Fig. 3h shows that the H1O3 distance shortens at high temperature which will lead to a temporary formation of H1O3 bond at
about 655 K and these two atoms will eventually bond to each
other at 690 K, indicating the adsorption of H1 to O3 after the
H1O2 bond cleavage. At higher temperature, H1 and O3 just
vibrate around their equilibrium positions.
Fig. 3i shows that the H2O2 distance nearly does not change
during the process of calefaction, indicating a steady bond. Com-

bining the changes of Fe1O2, Fe2O2, H2O2 and Fe2O2 distances, we can draw a conclusion that O2 transfers to Fe4 as a
hydroxyl group.
From the above analysis, we can get the following conclusions:
(a) a-FeOOH will dehydrate in the interval of 560655 K which is

Fig. 4. The formation and cleavage of bonds along the dehydration process.

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W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

in consistent with earlier ndings [1820]; (b) water molecule on

the surface of a-FeOOH is formed in the interval of 620655 K; (c)
water molecular will begin to cleave to H1 and O2H2 at 655 K,
and then H1 will transfer to O3 at about 655 K and bond to O3 at
about 690 K; besides, O2 will transfer to Fe4 at about 720 K as
O2H2 group.
Besides, from MD simulations, Fe2 O2 cleaved at about 425 K,
which may also happen in the interval of 425507 K and 538
645 K; whereas, H1 O1 breaks at about 552 K and Fe1 O2 bond
cleaves as the temperature hoisted to about 600 K. So during the
dehydration process, with the temperature rising, Fe2 O2 cleaved
at about 425507 K rstly, then H1 will move to H2O2 with the
formation of H2O Fe1 at about 560 K as shown in Fig. 4, and nally H2O will desorb from Fe1 at higher temperature with free H2O
formed.
Fig. 5 shows that the dehydration of a-FeOOH preferentially begins on the surface which is mainly due to water molecules formed

on the surface departs with less resistance than the interlayer

water. And the central core of a-FeOOH cannot further dehydrate
to a-Fe2O3 because water is prevented from escaping by the
increasing water pressure in the outer voids [18]. For the departure
of the interlayer water molecule, it must move along the direction
(0 1 0) (large tunnels) whose size seems large enough for water
molecules to leave as shown in Fig. 6. While, in the H and O atoms
migration or dehydration process, water will collide with other
ions or atoms and some water molecules will dissociate and bond
to them. Thus, thicker slabs will make the leave of water more
difcult.
In addition, from the nal structure of MD simulations (Fig. 5),
we can also observe the formation of pores at the place of OH
after losing water molecules during heating process. The dehydration process is associated with the formation of voids, which are
arranged in the a-FeOOH particles and are related to a-Fe2O3 formation. Fig. 5 also shows that during the dehydration process,

Fig. 5. The structure comparison of (a) a-FeOOH, (b) a-FeOOH obtained after dehydration between 300 and 600 K and (c) a-FeOOH obtained after dehydration between 600
and 900 K.

W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

the inner two layers do not have major breakdown of the atomic
patterns. The morphology of the particles does not change signicantly with respect to that of the original a-FeOOH after losing
water molecules at lower temperatures, which has also been
observed [64].
When heated at low temperatures, the removal of OH from
surface will form instantaneous vacancy. With the temperature
rising, other ions will move to the vacancy, which will lead to pore
in inner space, as a result of which the dehydration will proceed
from the outer surface to the inner centre. This is in agreement
with previous experimental results [18,65].
At 300900 K, Fe3+ has less rearrangement than O2 (Fig. 5) and
O2 can rearrange more quickly than Fe3+ which is in accordance
with previous experimental investigations [66]. This is mainly
due to that oxygen ions are smaller and lighter, and move faster
than iron ions and the positions of oxygen ions are of small shifts
during the dehydration. But the main modication from a-FeOOH
to a-Fe2O3 is due to the migration of iron ions in the interlayer
space to ll in tunnels at higher temperatures [19]. In other words,
the structure of the crystal is full of lattice distortion; even it is not
a real crystal of a-Fe2O3 after heating in the temperature range of
300900 K.
On the other hand, if the a-FeOOH did not dehydrate
completely, a certain number of H atoms and OH groups may
remain within the structure [67,68] which is due to the local defect
of hydrogen transfer process generated by a break of symmetry in
Fig. 2 appears as follows suggested [56]: H1 leaves with O2H2,
while H2 leaves with another O atom bonded to Fe4, then a
hydroxyl group remains in the crystal which may be responsible
for local crystalline defects.
3.3. Transition state simulation
We have calculated the energy barrier of hydrogen migration
from one hydroxyl group to adjacent one with the formation of
adsorbed water as shown in Fig. 7. In the transition state structure,
the distance of H1 O1 is 1.27 , H1 O2 is 1.30 , O2 Fe1 is 1.98

25

Fig. 7. Energy prole along the reaction coordinate of H migration.

and O2 Fe2 is 2.60 . H1 migration results in the cleavage of Fe2

and O2 in a concerted way, and then H1 will bond to O2 with
the formation of H2O Fe. Besides, there is only one imaginary frequency in the transition state. The calculated migration barrier is
118 kJ/mol, in close agreement with the previously experimental
value of about 114 kJ/mol [18], which strongly depends on crystallinity and particle size of the sample.
The second step is desorption of the adsorbed water molecule.
Our calculations show an energy increasing process along with
the elongation of the H2OFe distance without transition state.
After losing H2O, the energy is 82 kJ higher than the water adsorbed state. For comparison we have also computed the rst
water desorption energy (204 kJ/mol; or 178 kJ/mol after the correction of zero-point energy) of [Fe (H2O)6]3+, which is much higher
than the desorption of adsorbed water.
Since the barrier of hydrogen migration is 36 kJ/mol higher than
that of adsorbed water desorption, the dehydration mechanism of
(a-FeOOH) into hematite (a-Fe2O3) should be direct as suggested
[1519], and hydrogen migration should be the rate-determining
step.

4. Conclusions

Fig. 6. The size of the tunnel of a-FeOOH and size of H2O molecule.

Molecular dynamics (MD) simulations within the framework of

density functional theory have been carried to investigate the
dehydration process of a-FeOOH to a-Fe2O3 using VASP. It is found
that the employed theoretical models and methods are accurate in
simulating solids involving hydrogen bonds and are able to give
trends in dehydration processes. The calculated structures are in
excellent agreement with the observed ones.
The transformation begins preferentially on the surface of a-FeOOH and the dehydration is associated with formation of voids which
has been attributed to the loss of water during heating process.
From MD simulations, we can conclude that the dehydration
process involves in concerted hydrogen migration with the formation of adsorbed water and desorption of the adsorbed water molecule. The computed hydrogen migration barrier is 118 kJ/mol,
which is higher than energy cost (82 kJ/mol) of desorption of the
adsorbed water. Therefore, hydrogen migration is the rate-determining step, and this energetic difference suggests a direct transformation of a-FeOOH to a-Fe2O3 without the formation of any
intermediate. This work is just a step toward modeling the formation of a-Fe2O3. An understanding of the full transformation from
a-FeOOH to a-Fe2O3 may be applied to further investigations and
further interpretation.

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W.-J. Zhang et al. / Journal of Molecular Structure: THEOCHEM 950 (2010) 2026

Acknowledgments
The authors thank Prof. James D. Kubicki for helpful discussions
on the parameters setting for the optimization of a-FeOOH structure, as well as the National Natural Science Foundation of China
(Grant No. 20873173) and the National Outstanding Young Scientists Foundation of China (Grant No. 20625620) for supports. we
also thank Dr. Jianwen Liu (HU Berlin).
Appendix A. Supplementary data
The results of the benchmark calculations of bulk a-FeOOH are
included. Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.theochem.2010.
03.013.
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