Molecular Modelling at AWE

T he reaction of hydrogen with

uranium and plutonium is
important to both the nuclear power
the material towards further oxidation.
Thus, metal oxides are not only important
as the external surfaces of most metals,
equations and basic assumptions and
predicting physical and chemical
properties of the system in an ab initio
and nuclear weapons communities1. but also as materials in their own right. manner without regard to experimental
Given this fact, it is surprising how In order to quantify the hydrogen-uranium data. In this scenario, the rôle of
poorly understood this reaction actually reactions, it is necessary to understand experimental data is to provide a
remains. Although experimental work the mechanisms involved in gas transport means by which modelling results may
can provide us with valuable insight through the surface oxide layers. be validated, and not to predicate the
into the reaction mechanism, it can Specifically, one requires knowledge modelling. This can be achieved if one
never provide the full picture. To answer of the species of the gas involved in uses methods based on quantum
questions such as ‘which species of diffusion through the oxide, the diffusion mechanics, which enable the calculation
hydrogen diffuses to the metal surface’ rate and its temperature dependence, of structural, electronic and thermodynamic
requires the use of molecular modelling. the solubility of the gas species in the properties of materials and quantum
Here, we will illustrate some of these oxide and the mechanism by which it molecular dynamics, which enable
molecular modelling techniques and diffuses, e.g. via interstitial sites, vacancies transport properties and other time and
their application to uranium hydriding. or grain-boundaries within the oxide. temperature-dependent properties to
Our modelling studies here at AWE, at be calculated. Each of these techniques
Even ‘noble’ metals such as platinum Reading University and at Imperial has proven to be a very powerful predictive
develop some form of oxide coating College London are aimed at answering tool when applied to small systems
upon exposure to an oxygen-containing these questions using some of the containing only a relatively low number of
atmosphere. The phase and composition methods explained below. electrons. However the associated
of the surface oxide layer can greatly calculations rapidly become impossible
affect the reaction of the underlying Ab initio Calculations when the number of electrons increases
metal with gases, e.g. the oxide film on beyond approximately 500-1000. In fact,
the surface of aluminium acts as a barrier The most desirable approach to quantum molecular dynamics calculations
to oxygen transport through to the modelling a system involves using a set can even become intractable problems
metal surface and so rapidly passivates of physical constants, fundamental when this number is much smaller.

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 Discovery • The Science & Technology Journal of AWE

In addition to the problems encountered stoichiometric complexity. Thus, a when summed with the coulombic
with systems containing a relatively calculation of the diffusion coefficient interactions between charged species
large number of electrons, actinides of a hydrogen atom in UO2 would the energy of a particular configuration
contain f electrons that are problematic require a simulation cell that contained of the ions is calculable. In systems
in their own right for a number of reasons:of the order of 300 uranium ions which contain highly charged species,
(27,000 electrons), which far exceeds the van der Waals interactions
f electrons are quite diffuse in what is technically possible on today’s represented by the pair-potentials
nature, i.e. their associated super-computers. In fact, it is unlikely detailed above, contribute approximately
electron density is spread relatively that such calculations will be feasible 10% of the interaction energy of the
evenly over a large radius from the within the next ten years, even if system. Thus, small errors in the
nucleus, making overlap and computer power increases at the rapid pair-potentials in these systems can
consequent interaction with other pace it has in the past 20 years. easily be accommodated and will not
atoms and ions weak; be significantly detrimental to the quality
Molecular Modelling of the results2.
partially filled f shells lead to
Calculations
low-lying unoccupied states and Atomistic simulations include interactions
these cause convergence problems; Fortunately, one can simplify the between the electrons and nuclei
problem of calculating diffusion implicitly and not explicitly and are
the f electrons can be localised on coefficients and solubility curves for consequently thousands of times
an individual ion or spread over atoms and molecules in materials by quicker to perform on a system with an
several ions (itinerancy) which can setting up models of the system in equivalent number of atoms. Key to
change with charge state; which the atoms and ions are the success of atomistic simulations
represented by point charges which is the quality of the models for the
relativistic effects are very important interact with each other according to a individual ions (shell model or better,
to actinide electronic properties. set of functions or tabulated values. for example) and the pair-potentials
This affects the energetic ordering This approach, sometimes called between the ions, though in highly
of the orbitals and means that molecular modelling or atomistic charged systems the pair-potentials
spin-orbit coupling should be simulation, requires parameters for the are of lesser importance. In systems
included in the calculations since charge on each ion, or pair of charges containing uncharged atoms, such as
this will have a large effect on the for each ion in the shell model (Figure 1). hydrogen atoms, there are no permanent
spin properties of the actinide atoms The charge in the rigid-ion model is coulombic interactions, only instantaneous
or ions and magnetic properties of normally set to the formal charge on ones from temporary polarisation of the
the materials they constitute; the ion, but this is not always the case, atoms by charged ions in the vicinity of
and using partial charges on ions can the atom. In these cases the success of
many computer programs cannot lead to unpredictable results and is the simulations will rely heavily upon
handle f orbitals. another variable that needs to be the quality of the pair-potentials used
defined in the model. The interactions to describe the van der Waals interactions
A purely ab initio or quantum mechanical between the ions and atoms in the between the atoms and ions and on the
treatment of these systems is impractical. system are defined by a set of functions shell-model parameters for the atoms
The accurate calculation of diffusion representing the potential energy for themselves
coefficients and solubility curves of gas each combination of ions and atoms
atoms and molecules in ceramics at different separations; known as Atomistic simulations can be
requires models for the ceramic that pair-potentials since they act upon parameterised by a number of methods:
contain of the order of 1000 atoms; pairs of ions or atoms (Figure 2). These by fully quantum mechanical calculations
more if the oxide does not have a pair-potentials represent the van der of isolated systems such as pairs of
simple crystal structure or has a Waals interactions between species and ions or atoms; by semi-empirical

19
 calculations, such as electron-gas
Figure 1
calculations, on isolated systems
containing pairs of ions, where the
Core shell spring
electron density distribution of the ions
Shell model qcore
is fixed at some unperturbed value and
q shell by fitting to bulk properties of the
Rigid-Ion Model q material to be simulated, such as bulk
modulus elastic constants and
±
lattice energy. In systems such as
metal oxides the latter method is most
desirable since it guarantees that the
parameter set will reproduce the bulk
a) The rigid-ion model for ions and atoms, and b) the shell model for atoms properties of the material and thus its
and ions. In the rigid-ion model the charge on the point charge representing
response to external stimuli such as
the ion is normally the formal charge on the ion, but some parameter sets
isotropic and non-isotropic pressure
do vary.
b) In the shell model, the formal charge on the ion is usually the sum of
changes and heating. In systems
the charge on the core and shell, qion = qcore + qshell where no crystal structure data can
exist, such as hydrogen interactions
with an actinide oxide, the former two
Equation 1 methods must be applied to the problem.

Molecular modelling has been used to

Etotal = E coulombic + E bond + E rotation + E torsion + E vdW + ( E H −bond ) compute the energy of systems with
the ions being described by one or
other of the two models outlined
above. The Force-Field method relies
Equation 2 on the separation of energy terms into
component parts, each of which can be
equated to a physically meaningful
N −1 N
 qi q j e 2 
Ecoulombic = ∑ ∑ 4πε r 
o ij 
quantity (equation 1).
j =1 i > j
In the predominantly ionic systems
under investigation in this work, the
where: N=total number of ions
bond stretch term, Ebond, the bond
qi, qj = formal charge on ion x
rij = separation between ions i and j rotation term, Erotation, and the bond
torsion term, Etorsion, can be neglected
and only the coulombic term, Ecoulombic,
and van der Waals term, EvdW, need be
considered. The coulombic term takes
Equation 3 the form of the function that describes
the potential energy between two
charged particles, but summed over all
N −1 N   − r ij  B  possible pair interactions (equation 2).
E vdW =  −
ρ 
∑∑ A exp 
j =1 i > j 
  r ij6  This coulombic term converges only
very slowly as the separation between
ions increases, so a mathematical

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 Discovery • The Science & Technology Journal of AWE

method known as the Ewald summation

Figure 2
is used to model the interactions. This
requires three terms: a real space 5.0
cut-off distance; a reciprocal space cut-off
Atomic Separation ( Å) R
and an Ewald sum constant. The
mathematical formalism can be found 4.0
in standard textbooks3.
3.0
The van der Waals term can take one of
several forms, but the commonest of
these is the Buckingham potential shown D 2.0
in equation 3.
1.0
These functions produce a potential
φ
energy curve somewhat like that plotted
0.0
in Figure 2, having a potential minimum
of depth, Dφ, at some separation of φ

ions, Rφ. The repulsive part of the curve -1.0

0.0 2.0 4.0 6.0 8.0 10.0
comes from the exponential term in the
Potential Energy (kJmol -1 )
Buckingham function, and emanates
from the repulsion of electron gas A plot of the Buckingham potential
clouds around ions as they are brought
together. The attractive part of the
curve derives from the r-6 term and is Figure 3
a response to the dispersion forces
sometimes called van der Waals attraction.

Many properties that we wish to calculate

depend up time and temperature, but
molecular modelling as described
above only deals with static systems.
In order to calculate dynamic properties,
molecular dynamics simulations must
be carried out. These simulations
involve solving the Newtonian equations
of motion at very small time intervals
(time steps) to calculate the positions
of the atoms in a system as a series of
‘snapshots’ in time. Infinite systems
such as crystals can be examined by
using periodic boundary conditions, in
which the simulation cell is repeated on
all sides so that atoms leaving the cell
The periodic boundary condition as applied to a simulation of UO2-x. The
on one side are never lost to the system
simulation cell is surrounded by replicas of itself such that an oxide ion leaving
because they re-enter the cell from the
the cell on the left re-enters the central cell from the right hand cell
opposite side (Figure 3). The average

21
 kinetic energy that the atoms in the
Figure 4
system possess is determined by the
temperature at which the simulation is
carried out.

Molecular dynamics simulations allow

us to calculate properties of materials
such as diffusion coefficients, melting
temperatures and vibrational spectra.

X Example of the
Problems Addressed
The reaction of hydrogen with uranium
is a complex process that depends on
many variables, one of which is the
oxide over-layer1. The oxide that is
formed on uranium adopts the fluorite
structure which has an empty space at
its centre, known as an interstitial site
The unit cell of UO2, with uranium ions represented by blue spheres, oxide ions represented (marked by a green X in Figure 4).
by red spheres and the interstitial site indicated by a green cross Though it is known that the thickness
of the surface oxide layer influences the
rate of reaction of hydrogen with uranium,
Figure 5 it is not known what hydrogen species
is transported through the oxide layer
or the mechanism by which it diffuses.
It is important to understand these
factors in order to quantify the reaction
of hydrogen with uranium and we are
addressing these questions with our
molecular modelling studies.

We are investigating whether the hydrogen

diffuses via interstitial sites, vacancies
in the crystal or grain-boundaries of the
oxide. We have carried out molecular
dynamics simulations at a number of
temperatures of perfect crystals of UO2
with different species of hydrogen in
order to calculate the propensity of
hydrogen to diffuse via the interstitial
sites within the crystal (Figure 5).

Four unit cells of UO2, with uranium ions represented by blue spheres and oxide ions
We have built models of imperfect
represented by red spheres. Atom diffusion via interstitial sites as indicated by
curved arrow crystals of UO2 containing oxide vacancies

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 Discovery • The Science & Technology Journal of AWE

and hydrogen species and calculated

Figure 6
the diffusion coefficients using molecular
dynamics simulations at a range of
temperatures (Figure 6).

The lowest energy structures of 20

low Millar-index surfaces have been
determined by molecular dynamics
simulations at 300 K and this has
revealed that some surfaces are very
stable while some are very unstable as
created. Those that are the most stable
generally require little movement of the
atoms in the top five surface layers and
thus do not change much in appearance.
One such example of a naturally stable
surface is the [1 1 1] surface shown in
Figure 7. Higher energy surfaces, such
as the [4 2 0] shown in Figure 8, tend
to reconstruct to minimise the surface
energy. The reconstruction of the high Four unit cells of UO2, with uranium ions represented by blue spheres and
energy surfaces can lead to the formation oxide ions represented by red spheres. An arrow indicates the path of a
of microfacets, which are ‘mini-surfaces’ diffusing atom through an oxide vacancy site (indicated by a green dot)

on top of the main surface. In Figure 8

the [4 2 0] surface has reconstructed to Figure 7
form [1 1 0] and [1 0 0] ‘mini-surfaces’
on top leading to the saw-tooth effect
observed in this case.

A number of models of surfaces have

been combined to create models for
grain-boundaries in UO2 and used in
molecular dynamics simulations at 300K
to determine which are energetically
the most stable and might provide
pathways for hydrogen diffusion (Figure 9).

Recently we have carried out molecular

dynamics simulations of helium atoms in
our models for UO2 grain-boundaries
and determined activation barriers
from Arrhenius plots of the diffusion
coefficients at different temperatures
(Figure 10). These simulations allow us to
The calculated lowest energy structure of the [1 1 1] surface of UO2 at 300K
place an upper limit of the rates of diffusion
with the surface running horizontally perpendicular to the page
of hydrogen at different temperatures.

23
 Figure 8 Parameterisation of
Materials
The physical properties of actinide
materials define their response to
external stresses and strains imposed
by the environment and intrinsic
properties of the materials such as
self-diffusion, defect energies and
specific heat capacity. The oxides,
carbides and hydrides of plutonium and
the hydrides of uranium fall into this
category. Little experimental data are
available for these materials since they
are difficult to prepare pure, either in a
given stoichiometry or as a particular
allotrope, are difficult to handle, and, of
course, they are radioactive. Molecular
modelling studies of these materials
require physical properties to
The calculated lowest energy structure of the [4 2 0] surface of UO2 at 300K parameterise the models, but these
exhibiting the rumpling of microfaceting while the surface runs horizontally data are unavailable for the reasons
perpendicular to the page stated. Thus, they are ideal candidates
for pioneering ab initio computational
studies of their electronic, structural
Figure 9
and mechanical properties.

Workers at Reading University4 are

using plane-wave density functional
theory to calculate the ground-state
structures of plutonium oxides such as
PuO2, α-Pu2O3 and β-Pu2O3, and from
X X X these their mechanical properties such
as bulk modulus and elastic constants,
C11, C12 and C44. Very high cut-off
energies are required in simulations of
these systems, which are equivalent to
extremely high quality basis sets in
traditional ab initio calculations. This
requirement for high cut-off energies
means that these calculations are
extraordinarily computer resource
intensive and so Reading University
A model of the [1 1 0]-[2 2 1] grain-boundary of UO2, with uranium ions makes use of the super-computer
represented by blue spheres and oxide ions represented by red spheres. power at AWE. (See Box 1).
The grain-boundary runs horizontally across the page through the centre
of the picture. Three green crosses indicate channels running into the
page, down which diffusion can occur

24
 Discovery • The Science & Technology Journal of AWE

In Conclusion they test current methodology to its quantum mechanical methods and will
limits and we require state-of-the-art use this parameter set in our future
Molecular modelling allows us to probe computer software to carry out our simulations of hydrogen solubility and
materials that are difficult or dangerous simulations. diffusion in imperfect crystals and
to handle and assess conditions that grain-boundaries of uranium and
are impossible to achieve in the Our initial results suggest that both plutonium oxides. These simulations
laboratory. We routinely carry out molecular and atomic hydrogen are will contribute to both a better
simulations of radioactive materials immobilised in perfect crystals of UO2, understanding of the mechanism of
such as plutonium and uranium being trapped in the interstitial (vacant) hydrogen transport through actinide
oxides in order to determine diffusion sites of the lattice. Our current studies, oxides and data for numerical models
coefficients of atoms, ions and molecules however, with imperfect crystals, of uranium and plutonium hydriding.
at temperatures up to 3000 K, which surfaces and grain-boundaries of UO2 With every simulation, we are gaining
would be incredibly difficult to achieve indicate that helium atoms are much more information about materials that
in the laboratory. Our simulations more mobile in these non-ideal are technically very challenging to
are, however, very demanding of environments, with activation barriers experimentalists and theoreticians alike,
computational resources and require to diffusion in the range 20-80 kJmol . actinide oxides.
-1

the huge memory capacity and processor

speed of the AWE super-computers to We are currently defining a parameter
complete successfully. Not only are our set for hydrogen interactions with
calculations computer-intensive, but actinide oxides using high level

Figure 10

-21.0

He diffusion coefficients
-21.5
ln D(D in m 2s -1 )1/T (10 -3 K)

-22.0

-22.5

-23.0

-23.5

-24.0

-24.5

-25.0
0.6 0.8 1.0 1.2 1.4 1.6 1.8
Activation Energy = 25.9 kJmol -1+/- 2.5 kJmol -1

An Arrhenius plot of our helium diffusion data for the [3 2 1]-[2 2 1] grain-boundary in UO2

25
 Box 1

Computer Resources Figure 11

at AWE
At AWE we have two super-computers
which are constantly upgraded. A
massively parallel IBM SP3 super
computer5 shown in Figure 11 is equipped
with 1920 Power3 II processors, 2
Terabytes (2 million Megabytes) of
memory, and connected by Nighthawk II
network switches provides 3 TeraFLOPS
(3 x 1012 floating point operations per
second) of computing power. This
machine is used for calculations that
can be run in parallel and require a lot
of memory. Plane-wave DFT simulations
of actinide oxides typically run on 40 to
250 processors over a period of 2 to
14 days and require 20 to 120 Gigabytes
of memory!
The 3 TeraFLOPS IBM super-computer at AWE

AWE’s beowolf super-computer shown

Figure 12
in Figure 12 has recently been upgraded
to 2.8 GHz Pentium IV Xeon CPUs
delivering 1.2 TeraFLOPS with Gigabit
and Myrinet networking, 552 Gigabytes
of memory and 8.4 Terabytes of disk
space. This machine is used for serial
and parallel molecular dynamics
calculations up to 32 processors requiring
days or weeks of computational time.

The beowolf super-computer at AWE

26

Acknowledgements
The author wishes to thank Dr. Joseph 1
Glascott, AWE, Prof. Michael G.B. Drew
and Dr. Mark T. Storr, University of Reading
and the AWE super-computing staff of 2
Ash Vadgamma, John Dolphin, Mark
Roberts, Paul Tomlinson and Pete Brown.
References
J. Glascott, “Hydrogen and Uranium”,
Discovery, Issue 6, January 2003
R. W. Grimes, Imperial College,
London University, personal
communication
3 M. P. Allen and D. J. Tildesley,
“Computer Simulations of Liquids”,
Clarendon Press, Oxford
4 M. G. B. Drew, M. T. Storr and
D. W. Price, unpublished work.
5 A. Baxter, “New Supercomputer”,
Discovery, Issue 6, January 2003;
J. Taylor, “History of Computing”,
Discovery, Issue 3, July 2001
27
Discovery • The Science & Technology Journal of AWE
Author Profile
David can be contacted on
e-mail: David.Price@awe.co.uk
David Price
David was educated at Kingshurst
Comprehensive then Solihull Sixth
Form College before going up to
Keble College Oxford to read for a
BA(Hons) in Chemistry. He stayed
at Keble to read for a DPhil in
organometallic chemistry, which
encompassed synthetic, mechanistic
and molecular modelling work.
After post-doctoral spells in
Strasbourg and Munich, David
became a research fellow at the
University of Reading funded by
AWE. David joined the materials
modelling team at AWE in 2002
after spending eight years at
Reading University. He currently
works on the ageing of materials,
is a published author and is a full
Member of the Royal Society of
Chemistry and Chartered Chemist.