Nuclear Instruments and Methods in Physics Research B 239 (2005) 191–201

www.elsevier.com/locate/nimb

Threshold displacement energies in rutile TiO2:

A molecular dynamics simulation study
a,b,*
B.S. Thomas , N.A. Marks b, L.R. Corrales c, R. Devanathan c

a
Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Australia
b
School of Physics, University of Sydney, NSW 2006, Australia
c
Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA

Received 20 January 2005; received in revised form 6 April 2005

Available online 31 May 2005

Abstract

Threshold displacement energies are determined for Ti and O in rutile TiO2 using molecular dynamics simulations
with an empirical model. The simulations involve the introduction of a primary knock-on atom (PKA) with a range of
energies (30–150 eV) in various crystallographic directions at 160 K. We observe the formation of stable Frenkel
defects, as well as defect recovery via low-energy interstitial migration mechanisms. The latter causes significant statis-
tical variation between simulation outcomes, which leads to the definition of a defect formation probability. This prob-
ability is characterized as a function of PKA energy in order to define the threshold displacement energy and compare
with experimental results. Using a probability of 10%, the average threshold displacement energy is around 40 eV
for oxygen (comparable to experiment) and 105 eV for titanium. Using a probability of 50%, the values are 65 eV
and 130 eV respectively, which may be more appropriate for use in TRIM calculations. In addition, we run a parallel
set of calculations using a second empirical model, finding that the detailed results are highly model-dependent, partic-
ularly the oxygen defect structures and energies, which are compared to new ab initio data.
Crown Copyright
2005 Published by Elsevier B.V. All rights reserved.

PACS: 61.82.Ms; 61.80.Az; 61.72.Cc

Keywords: Rutile; Threshold displacement energy; Radiation damage; Computer simulation; Oxide

1. Introduction

Rutile is the most common form of TiO2. The

crystal structure is composed of TiO6 octahedra
*
Corresponding author. (Ti at the center and O at the corners), which
E-mail address: bse@ansto.gov.au (B.S. Thomas). share corners in the xy-plane and edges in the

0168-583X/$ - see front matter Crown Copyright
2005 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2005.04.065
192 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
Fig. 1. Crystal structure of rutile TiO2, projected along h0 0 1i.
Titanium atoms (light gray or blue) are inside shaded octahe-
dra, with oxygen atoms (dark gray or red) at corners. Black
lines indicate the unit cell. Colors refer to the web version of this
article.
z-direction, forming a one-dimensional channel
structure, as shown in Fig. 1. Rutile has been con-
sidered for various solid-state applications, partic-
ularly when doped via ion implantation. Rutile is
also present in synroc-type ceramics designed for
immobilization of high-level nuclear waste, and
many of the primary synroc phases consist of sim-
ilarly linked TiO6 octahedra. In fact, rutile itself is
being considered as a matrix for niche Tc-99
wastes [1]. The radiation response properties of
rutile are important for all these applications.
Radiation damage in rutile has been previously
studied experimentally using high-energy surface
bombardment with various ions, looking at lattice
disorder and annealing [2–7]. These studies show
that annealing of radiation-induced defects takes
place below 300 K in three stages (at 77 K,
150 K and 280 K), although no annealing of amor-
phized TiO2 occurs below 550 K [2]. Further, dam-
age accumulation in rutile samples irradiated at
160 K is much more rapid than at 300 K, indicat-
ing that point defects are highly mobile at room
temperature [3].
Experimental studies of radiation damage often
utilize the TRIM code [8] to calculate the stopping
distances of ions and to convert external irradia-
tion doses to units of displacements per atom
(dpa). TRIM is a Monte Carlo code, which pre-
dicts radiation damage in solids via the binary col-
lision approximation. The principal input
parameters for this code are the threshold dis-
placement energy (Ed) of each atom type in a par-
ticular solid and the density of the solid. Ed is the
minimum energy of a primary knock-on atom
(PKA) that produces a stable Frenkel defect on
its own sublattice. TRIM calculations of rutile
have previously used a threshold displacement
energy of 40 or 50 eV for both Ti and O ions,
based on the measured Ed of oxygen in MgO [9].
A recent experimental study of electron-irradiated
rutile suggests an oxygen displacement energy of
39 ± 4 eV [10]. Buck [11] estimated titanium dis-
placement energies in rutile by observing disloca-
tion loops produced during high temperature
electron irradiation, giving Ed(Ti)
50 eV. A
review by Zinkle [12] describes the importance of
accurate values of such parameters, which can be
different for each sublattice and crystallographic
direction. Displacement energies can be difficult
to measure experimentally, particularly for those
atoms that are less easily displaced, and many
disagreements on these values appear in the
literature.
Computational molecular dynamics is ideal for
calculation of threshold displacement energies,
since specific atomic processes can be viewed and
controlled directly. This means that single dis-
placement events may be considered on specific
sublattices in specific directions, in contrast to
experimental studies where many simultaneous
atomic displacements take place and only the sec-
ondary effects of defect formation may be mea-
sured. Although many computational studies
have been carried out using molecular dynamics
in metals and semiconductors, there are only a
few such studies in oxides, for example in MgO
[13], SiO2 glass [14], zirconolite [15] and zircon
[16,17]. This is partly due to the complexity of oxi-
des in terms of crystal structures and multiple
sublattices. Richardson [18] published an early
study describing molecular dynamics simulations
of threshold displacement energies in rutile, using
a small cluster of atoms and a limited range of
energies, which showed a considerable difference
in behavior between titanium and oxygen atoms.
Empirical models, molecular dynamics techniques
and computational power have advanced consid-
erably since that time. In this study we use empir-
ical molecular dynamics simulations to determine
threshold displacement energies for Ti and O in
rutile in various low-index crystallographic direc-
tions. We also consider the types of defects
 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
formed, and the mechanisms involved in Frenkel
pair recombination.
2. Molecular dynamics simulation methods
Empirical models have been used to study var-
ious atomic-level processes in ionic solids, includ-
ing the creation and migration of defects [19].
The model used here to describe TiO2 is from Mat-
sui and Akaogi [20]: a Buckingham-type rigid-ion
model, with partial charges on Ti and O. This
model accurately predicts the structures and prop-
erties of a range of TiO2 polymorphs [20,21],
including rutile surface formation, and is superior
to either formal-charge [21] or variable-charge [22]
models for TiO2. The rutile melting point and heat
capacity (at 1500 K) are also adequately repro-
duced by the Matsui model [23], and the predicted
thermal expansion of rutile at 300 K is approxi-
mately 2.5 · 105 K1, which is close to the exper-
imental value of 2.9 · 105 K1. The description of
the rutile structure using this model is not entirely
accurate, predicting axial elongation rather than
compression of TiO6 octahedra, but attempts by
the present authors to improve the model with
respect to the rutile structure resulted in compro-
mising other more important properties. In partic-
ular, the Matsui model correctly predicts rutile to
be the most stable polymorph of TiO2, whereas
many other models predict anatase or even a
quartz structure to be the lowest energy form.
Simulations of radiation damage involve sam-
pling atomic configurations that are far from equi-
librium, where the empirical model may be less
accurate. Properties such as thermal expansion
measure the performance of the model in predict-
ing elongated bonds, but shortened interatomic
distances (as in interstitial configurations) are
more difficult to test. In particular, Buckingham-
type pair potentials are generally not sufficiently
repulsive at the very short interatomic distances
sampled during atomic displacement events, and
must be splined with an appropriate short-range
potential. We use the ZBL [8] screened Coulomb
potential for each pair of atom types, with two dif-
ferent types of spline. For Ti–O and O–O we use a
cubic function (between 1.1 and 1.6 Å for Ti–O
193
and between 1.8 and 2.35 Å for O–O), which is
matched to the function values and first derivatives
at the endpoints. For Ti–Ti we use a Fermi
function:
F ðrÞ ¼ ð1 þ expðbf ðr  rf ÞÞÞ1 ð1Þ
1
with rf = 1.5 Å and bf = 4.0 Å , combined with a
cubic spline to the pure ZBL function between 0.6
and 0.7 Å to prevent the dispersion term from
dominating at small r.
Threshold displacement energies were deter-
mined by carrying out a series of molecular
dynamics (MD) calculations in which varying
amounts of kinetic energy were imparted to a sin-
gle PKA in a particular direction. This method has
been previously used to study metals, semiconduc-
tors and oxides. For each simulation, the evolution
of defects in the system was studied as a function
of time. The simulations were carried out using
the DL_POLY code [24], with modifications to
allow the introduction of a PKA with a variable
time step and a boundary layer thermostat. We
used a maximum time step of 1 fs (minimum sam-
pled time step 0.2 fs), and a 3.5 Å boundary layer
equilibrated at 160 K using a Gaussian thermostat.
Starting configurations were also equilibrated at
160 K. This temperature was chosen because there
are experimental data available at 160 K [3], and
defect accumulation occurs far more rapidly at
160 K than at 300 K [3]. A few calculations were
carried out at 300 K for comparison. Simulations
were run for 10 ps at constant volume in a super-
cell containing 4608 atoms, with a side length of
36 Å. Larger unit cells were used for Ti displace-
ments in channelling directions. For each PKA
atom type, direction and energy, 10 simulations
were run with different starting configurations, to
test for statistical variability. Additional simula-
tions were performed near the threshold. In total,
more than 800 trajectories were analysed.
3. Threshold displacement energies in rutile
3.1. System temperature and defect behavior
The temperature of the simulation cell is ele-
vated by the introduction of the PKA. For
194 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
example, a 100 eV PKA in a 4608-atom supercell
induces a temperature increase of 170 K. This ele-
vation in system temperature lasts only a fraction
of a picosecond, until kinetic energy is converted
into potential energy via collisions. After this, the
temperature remains elevated by around 60 K
for 0.5 ps, and then decreases over the following
1.5 ps to the original temperature, as the boundary
thermostat removes excess kinetic energy from the
edges of the cell.
After the introduction of the PKA, three phases
are observed in the temporal evolution of the sys-
tem, relating to defect formation and recombina-
tion. The PKA initiates the ballistic phase, which
lasts only a fraction of a picosecond and creates
many Frenkel defects. Subsequently, a thermal
spike (or gradient) is set up within the cell, with
the elevated temperature promoting annealing of
Frenkel defects, often within 0.5 ps of PKA intro-
duction and particularly in the region of the PKA;
we call this the fast diffusion phase. After the ther-
mal spike has relaxed (around 2 ps after PKA
introduction in this system), any remaining inter-
stitials undergo slower diffusion at the ambient
temperature, and recombination of Frenkel defects
takes place via probabilistic interstitial hopping
mechanisms – the slow diffusion phase. These sys-
tem evolution phases have been observed and
characterized in other systems [25,26]. The major-
ity (>75%) of defects that survive the fast diffusion
phase persist for the full 10 ps of simulation time at
160 K. In the slow diffusion phase, the recombina-
tion time of any existing Frenkel pairs depends on
the separation distance of the vacancy and intersti-
tial. Recombination time is also dependent on the
thermostat temperature, since interstitial mobility
is temperature-dependent. At 160 K, a defect
remaining after 2 ps is more likely to persist for
10 ps than at 300 K, where interstitial mobility is
higher. For this reason, only the results from
160 K simulations are reported.
3.2. Threshold displacement energy
The TRIM code defines threshold displacement
energy (Ed) as the minimum energy required to
knock a target atom far enough away from its lat-
tice site such that it will not immediately return. In
this study we define a stable defect as one that per-
sists for at least 2 ps, which is at the beginning of
the slow diffusion phase, after the thermal spike
has relaxed. This is comparable to the simulation
time used by Park et al., for determining threshold
displacement energies in MgO [13]. With this defi-
nition we study only primary damage creation and
ignore the effects of long-term defect annealing.
Further, we only consider defects on the same
sublattice as the PKA. In general, displacement
energies below 150 eV produce only one stable
Frenkel pair; exceptions are oxygen displace-
ments in h1 0 1i, where two pairs can be temporar-
ily produced.
Using this definition of a stable defect, Ed is
determined by finding the onset of stable defect
formation with increasing PKA energy. However,
we find that for any given PKA atom with a given
energy in a particular direction, multiple simula-
tions with different starting configurations give
very different results, due to the random thermal
motions of atoms and migration of interstitials
during the thermal spike phase. This statistical
variation creates significant ambiguity in Ed val-
ues, even at the low temperature of 160 K. We
define the defect formation probability (DFP) as
the fraction of displacement events resulting in a
stable defect, which is a function of crystallo-
graphic direction and PKA energy. Mota et al.
[14] use a similar definition in their study of silica
glass but the probability is averaged over all direc-
tions. No probabilistic effects have been reported
for crystalline oxides. Fig. 2 shows the DFP as a
function of PKA energy for oxygen in two repre-
sentative directions: h0 0 1i and h1 0 0i.
In general, DFP increases with PKA energy,
but there is not a sharp threshold for either atom
type in any direction. This is due to the formation
and recombination of metastable Frenkel pairs,
and results in an ‘‘uncertainty band’’, as defined
by Malerba and Perlado in SiC [27], which repre-
sents energies at which a stable defect may or
may not be produced. Further, the DFP for oxy-
gen in h1 0 0i (as well as some other directions) dis-
plays a decrease with increasing energy after the
initial increase, which is not easy to explain. This
decrease may be due to annealing effects as the
temperature increases with PKA energy; it is more
 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201 195

1.0 Table 1
Threshold displacement energies of oxygen and titanium atoms
Ο 〈001〉 in rutile, in various principal crystallographic directions, as
Defect formation probability

0.8 defined using a given threshold defect formation probability

(DFP)
0.6 Direction Threshold displacement energy (eV)
Oxygen Titanium
0.4 DFP 10% DFP 50% DFP 10% DFP 50%
h0 0 1i 65 85 70 80
0.2 h1 0 0i 30 50 110 115
h1 1 0i 55 60 95 100
h1 0 1i 30 60 105 140
0.0
0 20 40 60 80 100 120 140 160 h1 1 1i 35 70 115 160

1.0 Weighted 40 65 105 130

average
Ο 〈100〉
Defect formation probability

0.8 Values are quoted within ±5 eV. See text for definition of
weighted average.
0.6

number of symmetrically equivalent displacement

0.4
0.2
0.0
0 20 40 60 80 100 120
PKA energy (eV)
Fig. 2. Probability of stable defect formation for an oxygen
PKA in h0 0 1i and h1 0 0i.
pronounced in directions where the PKA under-
goes glancing collisions rather than direct knock-
ons, leading to a larger local disordered zone.
Alternatively, the decrease in DFP with increasing
energy (including zero values) may be statistically
insignificant, and a much larger number of simula-
tions may lead to a smooth increase in DFP with
energy. Given this complex behavior, there are
many possible definitions of the threshold dis-
placement energy. We use the defect formation
probability to define Ed, using two different prob-
ability thresholds: 10% and 50%. The first repre-
sents the onset of damage and the second
represents the point at which half of the displace-
ment events result in stable defects. The resulting
threshold displacement energies for oxygen and
titanium atoms in principal crystallographic direc-
tions are shown in Table 1. The multiplicity of
each direction is also calculated, based on the
directions in a single unit cell, and is used to calcu-
late a ‘‘weighted average’’ Ed for each atom type.
Note that particular directions in the xy-plane do
not have inversion symmetry; for example, h1 0 0i
and h1 0 0i are symmetrically inequivalent for each
140 160
oxygen atom. In these cases, the lowest threshold
is quoted.
The lower (DFP 10%) threshold displacement
energy for oxygen compares favorably with the
experimental value of 39 ± 4 eV. This is reasonable
given that the experiments measure the onset of
radiation-induced defect formation. The experi-
mental data for titanium are less reliable; Buck
reports a value of 45–50 eV [11] from observations
of dislocation loops resulting from electron irradi-
ation. This is about half the value reported here,
but may not be truly comparable due to the multi-
ple displacement events sampled in the experiment
and interference from oxygen displacements,
which are almost certainly taking place at these
energies. Earlier computational results [18] and
experimental data from other titanate systems
[28] support the use of a higher Ed value for tita-
nium. Interestingly, the directional dependence of
Ed for Ti calculated here corresponds well to the
experimental results of Buck [11] and the simula-
tions of Richardson [18].
Both oxygen and titanium displacement energies
display some anisotropy with crystallographic
196 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
direction. For oxygen, the h0 0 1i direction is the
only one in which a direct knock-on with another
oxygen atom occurs; the other directions result in
glancing collisions with other oxygen atoms, of
which the h1 1 0i direction is the least densely pop-
ulated. No channelling is observed on the oxygen
sublattice; oxygen trajectories are quickly deflected
and the PKA energy dissipated among many other
atoms. Nonlinear replacement sequences are pre-
ferred as a means of both Frenkel pair formation
and recombination. In contrast, Ti is most easily
displaced in the h0 0 1i direction, where a direct col-
lision with a neighboring Ti atom results in a
focussed linear collision sequence. Displacements
in this direction produce a much larger separation
of vacancy and interstitial for a given PKA energy
compared with Ti displacements in defocussing
directions. There is a similar channelling effect
observed in h1 0 0i, where there are no oxygen
atoms separating titanium nearest neighbors (as
for h0 0 1i); however, the neighbor distance is larger
than in h0 0 1i, which reduces the channelling effect,
as observed experimentally [5]. The Ti threshold is
much higher than the O threshold, due to its higher
lattice binding energy and the larger electrostatic
attraction between vacancy and interstitial. Also,
the titanium PKA energy is easily transferred to
multiple neighboring oxygen atoms, which can
result in the formation of oxygen Frenkel pairs; this
not only contributes to the higher Ed for Ti, but
also implies that experimentally determined Ed val-
ues for Ti may be too low, since titanium and oxy-
gen displacements cannot be easily decoupled.
These results show that there is a large differ-
ence in behavior between Ti and O atoms, as well
as some directional dependence for each atom
type. Neither of these effects is accounted for in
TRIM calculations of rutile to date. Anisotropy
cannot currently be incorporated into TRIM, but
we can use more appropriate average threshold
displacement energies that distinguish Ti and O.
We recommend a value of 65 eV for oxygen and
130 eV for titanium, based on a defect formation
probability of 50%. Some tests were carried out
in non-principal directions to test these values,
and they appear to be reasonable. Using these
new values, we perform a TRIM calculation to
compare the number of titanium vacancies pro-
duced by 360 keV Xe2+ ions with that reported
by Li et al. [6], who used Ed = 50 eV for both Ti
and O. The increase from 50 eV to 130 eV reduces
the number of titanium interstitials by 60%, giving
a value of 300 Ti vacancies per ion, which is still
about triple the estimated experimental value
reported by Li et al. [6] at room temperature. Since
the TRIM code does not include any thermal
effects, the difference may be attributable to recom-
bination of Frenkel pairs (annealing) at room tem-
perature, including the effects of cascade overlap,
as Li et al. suggest [6]. However, the defects ob-
served in simulations may not always be detectable
in experiments. In fact, the experimental value re-
ported by Li is only a crude estimate, based on
dechannelling of He+ ions beneath the surface.
The computational value is probably more reliable
for bulk irradiation, neglecting Frenkel pair
recombination. For oxygen, an Ed of 65 eV
reduces the number of oxygen interstitials by
25% compared to the standard value of 50 eV.
4. Defect configurations and model dependence
The accuracy of these Ed values relies on the pre-
dicted behavior of defects. We find that Frenkel
pairs can recombine from quite large separations
(more than a few unit cells), depending on their ori-
entation, giving rise to defect formation probabili-
ties between zero and one. This recombination is
thermally assisted, and occurs via replacement se-
quences of interstitials, which are generally nonlin-
ear except for titanium in h0 0 1i and h1 0 0i. It is
beneficial to test the accuracy of the predicted
defect structures, in order to affirm the predicted
migration mechanisms. Ideally, we would also
check the accuracy of the interstitial migration
energy barriers but this is far more computationally
intensive. In this section, we compare the defect
configurations calculated with the Matsui model
with those obtained using a different empirical
model for rutile, and also with new ab initio data.
4.1. Matsui model
Two types of interstitial defect are observed for
both Ti and O atoms using the Matsui model: the
 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
split interstitial, where two identical atoms share a
single lattice site in a dumbbell-like configuration,
and the channel site, where the interstitial atom re-
sides in the center of the rutile channel. Fig. 3
shows both split and channel configurations for
an oxygen interstitial. Oxygen interstitials form
mostly split interstitials while Ti interstitials prefer
the channel sites. The anion split interstitial config-
uration has been previously observed in calcula-
tions of rutile-type NiF2 [29]. In the case of Ti
interstitials there are additional structural variants,
including some configurations involving more than
two atoms. No antisite defects are observed, due to
the strong electrostatic interactions.
Migration of oxygen interstitials is observed to
take place from split interstitial to split interstitial
via channel sites, which lie halfway between atomic
layers. This enables motion in all three dimensions,
but favors the xy-plane. A similar mechanism was
postulated for rutile-type NiF2 [29]. The migration
energy is estimated from static and dynamic calcu-
lations at <0.1 eV, indicating that annealing of
Frenkel defects is likely to occur well below room
temperature, as observed in experiments [2].
Migration of Ti interstitials is more anisotropic;
in h0 0 1i Ti interstitials move directly from channel
site to channel site, whereas in the xy-plane chan-
nel sites are connected by split interstitials in the
plane and also by coordinated movements involv-
ing many Ti atoms – see Fig. 4. The migration
energy barrier is estimated at 0.3 eV using the Mat-
sui model. Vacancies are immobile on the time-
scale of the simulations.
The Frenkel pair recombination distance is also
estimated for both titanium and oxygen defects.
This is the minimum distance separating an inter-
stitial and vacancy such that they will not sponta-
Fig. 3. Oxygen interstitial configurations: (a) split interstitial (z = 0), (b) channel interstitial (z = 0.25), (c) channel-wall interstitial
(z = 0.5), as calculated for an isolated interstitial using the Matsui model. Smaller (dark gray or blue) atoms are titanium; larger (mid-
gray or red) atoms are oxygen. Colors refer to the web version of this article.
197
Fig. 4. Migration of Ti interstitials in h1 0 0i. Smaller (dark gray
or blue) atoms are titanium; larger (mid-gray or red) atoms are
oxygen. The arrow indicates the position of the Ti vacancy.
Colors refer to the web version of this article.
neously recombine. For each displacement
simulation we identify the most widely separated
Frenkel pair and determine whether or not the
vacancy and interstitial recombine within 2 ps. If
the defect rearranges to form another stable defect
configuration, this is not considered as recombina-
tion. From this we calculate the defect recombina-
tion probability for each distinct Frenkel pair
configuration (irrespective of the direction or en-
ergy of the PKA that produced it); for many indi-
vidual defect configurations, recombination occurs
in some cases but not in others. This recombina-
tion probability is shown in Fig. 5 as a function
of Frenkel pair separation, for both oxygen and
titanium Frenkel pairs. Titanium Frenkel pairs
oriented in h0 0 1i are considered separately since
they behave quite differently to other Ti Frenkel
pairs. Only defect configurations that occur more
than twice over the entire set of displacement sim-
ulations are included in the plot, to minimise
errors.
The lines in Fig. 5 are Fermi functions (see Eq.
(1)) with a fixed bf value of 1.0 Å1 and fitted rf
values. We take the rf value, which represents 50%
probability of defect recombination, to be the
198 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
1.0
Recombination probability
0.8
0.6
0.4
0.2
0.0
0 2 4 6 8 10
Frenkel pair separation (Å)
Fig. 5. Probability of Frenkel pair recombination as a function
of vacancy-interstitial separation distance, for both oxygen and
titanium. Titanium Frenkel pairs oriented in the h0 0 1i direc-
tion are shown separately. The curves are fitted Fermi functions
(see text); from left: oxygen, Ti (other) and Ti h0 0 1i.
Frenkel pair recombination distance. This gives an
oxygen Frenkel pair recombination distance of 7.1
Å; there is little dependence on the orientation of
the Frenkel pair, despite the scatter in the data.
The titanium Frenkel pair recombination distance
is 12.7 Å for a pair oriented in h0 0 1i (resulting
from a displacement in this direction), but only
9.6 Å for all other titanium Frenkel pairs, with lit-
tle further dependence on orientation. The reason
for this difference in Ti defects is that migration
of Ti interstitials is favored in the h0 0 1i direction.
These recombination distances can be used to
approximately include the effect of spontaneous
defect recombination in simple binary collision
calculations such as TRIM, both within a single
cascade and also in regions of cascade overlap,
which will reduce the predicted number of defects
formed. Note that the recombination distance is
temperature dependent; at higher temperatures
(for example, induced by higher PKA energies),
recombination distances can be much larger than
at lower temperatures.
4.2. Alternative formal charge model
For comparison, we repeat a subset of the MD
displacement simulations using the formal charge
model of Catlow, Freeman and Royle [30]
(CFR). This is the best available formal charge
model for rutile, accurately reproducing the elastic
Oxygen constants at the expense of the unit cell dimen-
Ti 〈001〉
sions; the predicted c-parameter is 8% too long
Ti (other) (as described in the Collins review paper [21]). It
should be noted also that this model (like many
other rutile models) incorrectly predicts the quartz
structure to be more stable than the rutile structure
for TiO2, which creates problems when simulating
higher energy cascades due to local melting and
recrystallization.
We use the CFR model as a rigid ion model
12 14 16 18 (without the polarizing shells), which affects the
polarization properties, including the dielectric
constant, but not the predicted structure or elastic
constants of pristine rutile. As with the Matsui
model, the Buckingham potentials are splined with
the ZBL potential at very short interatomic dis-
tances, using Fermi functions for Ti–O and Ti–Ti
potentials and a combination of Fermi and cubic
functions for O–O. We note that inclusion of the
polarizing shells in this model affects the absolute
defect energies, but retains the order of defect sta-
bility. Catlow et al. [30] reported defect energies
for this model but the configurations of the defects
are not specified. We do not expect to reproduce
their values due to the removal of shells and also
to the short-range ZBL spline, which significantly
affects the predicted structures and energies of
interstitials.
MD simulations of displacements using the
CFR model reveal defect behavior that is vastly
different to the behavior predicted by the Matsui
model, particularly for oxygen interstitials and
vacancies. The preferred structure of oxygen inter-
stitials is entirely different: the oxygen interstitial
resides within the channel wall, displacing nearby
oxygen atoms in the z-direction; we call this the
channel-wall interstitial, which is shown in Fig.
3(c). There are in fact two distinct channel-wall
interstitial configurations that are very close in
energy (within 0.2 eV): the oxygen interstitial can
reside halfway between two channel-wall oxygen
ions in the z-direction (as shown in Fig. 3), or
two oxygen atoms can share a single site, being
separated in the z-direction (‘‘split-channel-wall’’).
As a result of these two channel-wall defects, the
oxygen interstitial migrates easily in the z-direction
but does not migrate in the xy-plane on the time-
 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201 199

scale of the simulations. Hence, both the magni-
tudes and the directional anisotropy of threshold
displacement energies predicted with this model
are different to those predicted using the Matsui
model. The weighted average Ed for oxygen (using
50% DFP) is estimated at 40 ± 10 eV, which is sig-
nificantly lower than the value calculated using the
Matsui model, due primarily to the lack of intersti-
tial migration in the xy-plane. For the same rea-
son, the CFR model predicts much narrower
uncertainty bands than the Matsui model in all
directions except h0 0 1i.
The behavior of isolated titanium defects is sim-
ilar between the two models, but the differing
behavior of the surrounding oxygen atoms affects
the directional anisotropy of the titanium displace-
ment energies. For titanium, the directional aniso-
tropy measured experimentally by Buck is in
agreement with the Matsui model predictions. The
weighted average Ed for titanium is 115 ± 10 eV
using the CFR model, which is not too different
from the Matsui model predictions.
4.3. Ab initio defect calculations
In order to justify the use of the Matsui model,
we calculate the structures and energies of the
three types of oxygen interstitials (split, channel
and channel-wall) using the density functional the-
ory (DFT) code VASP [31], with projector aug-
mented-wave potentials [32] and the generalized
gradient approximation [33]. Frenkel pairs are cal-
culated in a 2 · 2 · 3 supercell (72 atoms) by plac-
ing an interstitial and a vacancy within the same
cell to preserve charge neutrality, with vacancy
and interstitial separated by as large a distance
as possible within the cell, while maintaining sta-
bility. For comparison, we use the General Utility
Lattice Program [34] (GULP) to calculate the cor-
responding defect supercell energies using the Mat-
sui and CFR rigid-ion models, as splined with
ZBL. It is important to include the short-range
spline in these static calculations in order to facil-
itate accurate comparison with molecular dyna-
mics simulation results; the short-range ZBL
spline makes a significant difference to both struc-
tures and energies of interstitial configurations.
Supercell calculations are performed at the equilib-
rium rutile cell volume for each method, allowing
full relaxation of atomic positions. For the oxygen
channel interstitial, the positions of the interstitial
atom and the titanium atom at the origin are not
allowed to vary, to counteract instability due to
the asymmetry of the cell. For the oxygen chan-
nel-wall interstitial we use the split version, since
it is more stable in the small supercell. For refer-
ence, we also use GULP to calculate the oxygen
Frenkel pair energy for an infinitely-separated
vacancy and interstitial pair, for each interstitial
type, using the Mott–Littleton [35] method and
the Matsui model only.
Table 2 shows the calculated energies of the
three types of oxygen close Frenkel pairs using
DFT, the Matsui model and the CFR model, as
well as the infinitely-separated Frenkel pair ener-
gies using the Matsui model. Note that the abso-
lute energies do not reflect the true Frenkel pair
formation energies due to the small unit cell and

Table 2
Oxygen Frenkel pair defect energies for three interstitial configurations (split, channel and channel-wall) in 2 · 2 · 3 rutile supercells,
using density functional theory (DFT) and two empirical models: Matsui and CFR; the energy of an infinitely-separated Frenkel pair
(1) is also given for the Matsui model. DE is the energy difference between successively-listed interstitial configurations
Defect energy (eV/pair)
DFT CFR Matsui Matsui (1)
E DE E DE E DE E DE
Split 4.7 Unstable 7.6 9.0
0.5 – 0.5 0.2
Channel 5.2 7.9 8.1 9.2
0.4 2.8 0.6 1.3
Channel-wall 5.6 5.1 8.7 10.5
200 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
the proximity of vacancy and interstitial; they are
provided for comparison of identical defect config-
urations between the different methods. This is
also true of the relative energies, with the addi-
tional reason that the Frenkel pair separations dif-
fer between the different defect types. This is
illustrated by the difference between the close and
infinitely-separated Frenkel pair energies using
the Matsui model, although the order of stability
is maintained.
Using the CFR model the split interstitial is
unstable and spontaneously recombines or rear-
ranges to form a channel-wall interstitial. All the
other oxygen defect configurations are stable with
each method. The Matsui model predicts struc-
tures in much closer agreement with DFT results
(all atomic positions within 0.3 Å) than the CFR
model. In particular, the CFR-predicted vacancy
structure is a ‘‘split vacancy’’, where an oxygen
atom neighboring the vacant site shifts to midway
between the two sites. This is very different to the
DFT and Matsui results, which show only minor
perturbations around the vacancy. For the split
interstitial, DFT predicts the two oxygen atoms
to be essentially in the xy-plane; the Matsui model
prediction is slightly out-of-plane, although the
infinitely-separated split interstitial configuration
is in-plane.
From the energies in Table 2 it is clear that nei-
ther empirical model accurately predicts absolute
defect energies for close Frenkel pairs, with respect
to our calculated DFT values. However, the Mat-
sui model predicts relative energies that are in very
good agreement with the DFT results. This gives
us confidence that the oxygen defect behavior is
well-described by the Matsui model, and therefore
that the calculated threshold displacement energies
are reliable.
We also performed a VASP calculation of a
titanium Frenkel pair in a 2 · 2 · 3 supercell, using
a channel interstitial and a vacancy at a distance of
(a/2, a, 3c/2), giving an energy of 4.0 eV. This is
comparable to energies of similar structures calcu-
lated using DFT by He and Sinnott [36]. Using the
same defect supercell, the Matsui model predicts
relaxed atomic positions within 0.3 Å of those cal-
culated using DFT. In contrast, the CFR model
predicts Ti interstitial and vacancy structures that
highly perturb the surrounding lattice, making
the defect unstable within the small cell. The en-
ergy predicted by the Matsui model is about three
times the DFT value; this discrepancy may be
attributable to atomic polarizability and charge
transfer effects, which are not accounted for in
the empirical models used in this work. For an
infinitely-separated titanium Frenkel pair, the
Matsui-predicted defect energy is
18 eV. At infi-
nite separation the CFR model predicts the Ti
Frenkel pair to be stable, but again with large per-
turbations of the lattice.
From this comparison of models, we can see the
importance of defect behavior in the simulation of
radiation damage response properties and the pit-
falls of using an inadequate model, as well as the
need for accurate calculations of defect structures
and energies.
5. Conclusions
We have determined threshold displacement
energies in rutile TiO2 using molecular dynamics
simulations with an empirical partial charge
model, as well as characterizing defect forma-
tion and migration behavior. Oxygen interstitials
migrate via long nonlinear replacement sequences
with low migration energy barriers, resulting in
annealing of Frenkel pairs below room tempera-
ture, in accordance with experimental results [2].
On the titanium sublattice we observe channelling
in the h0 0 1i direction, and to a lesser extent in the
h1 0 0i direction. We also find that the choice of
empirical model has a large impact on the pre-
dicted defect structures and energies, which in turn
affect the description of both the primary damage
state and defect recovery. We have calculated the
energies of some important defect configurations
in rutile using DFT, and confirm that the Matsui
partial charge model is appropriate for simulating
radiation effects in rutile TiO2.
The Ed values recommended for TRIM calcula-
tions, as determined in this work, are 65 eV for
oxygen and 130 eV for titanium, representing the
energies at which there is a 50% probability that
a stable defect will be formed. These new Ed values
are higher than those previously used, which may
 B.S. Thomas et al. / Nucl. Instr. and Meth. in Phys. Res. B 239 (2005) 191–201
be due in part to the predicted formation of meta-
stable defects in rutile, leading to defect formation
probabilities between zero and one for a large
range of energies. For titanium, there is no reliable
experimental Ed value, and the use of our calcu-
lated value in TRIM calculations leads to a 60%
reduction in the predicted number of defects. This
new titanium Ed may be a good first approxima-
tion for other titanium oxide materials with similar
structures, and certainly indicates that using iden-
tical Ed values for cations and anions is inappro-
priate in oxides.
Acknowledgements
B.S.T. would like to thank B.D. Begg and E.R.
Vance for helpful discussions and comments on
the manuscript. L.R.C. and R.D. were supported
by the Office of Basic Energy Sciences, US Depart-
ment of Energy. Battelle operates Pacific North-
west National Laboratory for the US
Department of Energy.
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