phys. stat. sol. (b) 245, No. 12, 2800– 2807 (2008) / DOI 10.1002/pssb.

200844142

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basic solid state physics
Structural, electronic and optical
properties of spinel MgAl2O4 oxide
S. M. Hosseini*

Department of Physics (Materials and Electroceramics Laboratory), Ferdowsi University of Mashhad, Iran

Received 6 April 2008, revised 13 May 2008, accepted 25 June 2008

Published online 8 August 2008

PACS 71.15.Mb, 71.20.–b, 78.20.Ci

*
e-mail sma_hosseini@yahoo.com, Phone: +98 511 8435723, Fax: +98 511 8796416

The structure, band structure, total density of states, dielectric performed for the energy range 0 – 40 eV. It is shown that the
function, reflectivity, refractive index and loss function have material is transparent at visible wavelengths and the disper-
been calculated for spinel MgAl2O4 oxide using density func- sion curve of the refractive index is fairly flat in the long-
tional theory. The full-potential linearized augmented plane wavelength region and rises rapidly towards shorter wave-
wave method was used with the generalized gradient ap- lengths. The refractive index is 1.774 at 800 nm near the
proximation. Calculations of the optical spectra have been visible region.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction The spinel structure (sometimes words, the composition with respect to one unit cell can be
called garnet structure) is named after the mineral spinel (A8)(B16)O32 or A8(B8A8)O32 = A(AB)O4 in regular chemi-
(MgAl2O4); the general composition is AB2O4. The spinel cal notation, or (A8/3B16/3)(A16/3B32/3)O32, and so on, with the
structure has a close-packed face-centred cubic structure of atoms in the parentheses occupying the respective site at
space group Fd3m (number 227), with eight MgAl2O4 units random. Two types of spinels can be distinguished: normal
per cubic cell [1]. Three degrees of freedom associated and inverse spinels. In the normal spinel, all Al3+ ions are
with the detailed atomic arrangements of spinels are: in octahedral coordination with local symmetry D3d, and all
(i) the lattice parameter, a; (ii) the anion parameter, u; and Mg2+ ions are in tetrahedral coordination with point group
(iii) the cation inversion parameter. The cations (usually symmetry Td. Thus the general formula may be written as
metals) occupy 1/8 of the tetrahedral sites and 1/2 of the (Mg)[Al2]O4 or (Mg8)[Al16]O32 for the cubic cell, where ( )
octahedral sites and there are 32 oxygen ions in the unit and [ ] denote tetrahedral and octahedral sites, respectively.
cell. The anion sublattice is arranged in a pseudo-cubic The Mg–O and Al–O bond lengths in the normal spinel
close packed (ccp) spatial arrangement. Some spinels pos- are 1.967 Å and 1.855 Å, respectively [3]. MgAl2O4 single
sess almost ideal ccp anion sublattices. The description of crystals are widely used for bulk acoustic wave and mi-
the atomic positions in spinel is dependent on the choice of crowave devices and fast IC epitaxial substrates. It is also
setting for the origin in the Fd3m space group. Two differ- found that MgAl2O4 is a good substrate for III–V nitride
ent equipoints with point symmetries 4 3m and 3 m are pos- devices [4].
sible choices for the unit cell origin. Moreover, the origin The spinel oxides comprise an important class of ce-
can be assigned to either a vacant site or an occupied lat- ramic compounds with a variety of interesting electrical,
tice site. The coordinates of the anions at equipoints 32e magnetic and optical properties. The magnesium spinel
are not special: they vary according to a single parameter, MgAl2O4 has a combination of desirable properties of high
u for a perfect ccp anion arrangement, uideal43m
= 3/ 8 (0.375) melting point (1250 °C), high strength, resistance to
and uideal = 1/ 4 (0.250) for origins at 4 3m and 3 m, respec-
3m
chemical attack and low electrical losses [5]. These special
tively [2]. properties mean that a magnesium spinel has many impor-
The spinel structure is very flexible with respect to the tant applications. It has been reported that MgAl2O4 thin
cations it can incorporate; there are over 100 known com- films show interesting characteristics in terms of their use
pounds. In particular, the A and B cations can mix. In other in humidity measurement devices [6, 7].

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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phys. stat. sol. (b) 245, No. 12 (2008) 2801

A few computational approaches have also been made

to investigate the structure and the electronic structure of
spinel MgAl2O4 such as lattice constants, internal oxygen
position and band gap. Wei and Zhang [8] have used a
first-principles band-structure method. They have system-
atically studied the cation distribution in closed-shell
AIIB2IIIO4 and AIVB2IIO4 spinels where the group II atoms are
Mg, Zn and Cd, the group III atoms are Al, Ga and In and
the group IV atoms are Si, Ge and Sn. The total energies,
the structural parameters and the band gaps of these com-
pounds in both normal and inverse spinel structures have
been calculated. Mo and Ching [3] have studied the elec-
tronic structure of normal, inverse and partially inverse
spinels in the MgAl2O4 system by means of first-principles Figure 1 (online colour at: www.pss-b.com) Primitive tetra-
calculations. Catti et al. [9] have calculated the ground- hedral unit cell of spinel MgAl2O4. The cubic cell consists of
state crystal energies of cubic MgAl2O4 (spinel), MgO eight constants of type I and II.
(periclase) and rhombohedral α-Al2O3 (corundum) at dif-
ferent volumes, relaxing the corresponding structure, by
the all-electron periodic Hartree–Fock method (CRYS- the symmetry of the diamond structure. However, they dis-
TAL program). Khenata et al. [10] have studied theoreti- rupt the cleavage as there are no cleavage directions in any
cally the structural, elastic and electronic properties of member of this group.
spinel MgAl2O4 and ZnAl2O4 oxides using the full- The primitive tetrahedral unit cell of spinel MgAl2O4 is
potential linear augmented plane wave (FP-LAPW) illustrated in Fig. 1. Inside the cell, with eight formula
method as implemented in the WIEN97 code. In this ap- units per cubic cell, each magnesium ion is tetrahedrally
proach the local density approximation (LDA) was used coordinated to four oxygen atoms while each aluminium
for the exchange-correlation (XC) potential. Sampath et al. atom is surrounded by six octahedrally distributed atoms.
[11] studied the electronic structure of zinc aluminate The structure consists of eight octants of type I and type II
(ZnAl2O4) and zinc gallate (ZnGa2O4) by the self-con- as shown in Fig. 1. The type I octants contain magnesium
sistent tight-binding linearized muffin-tin orbital method ions in tetrahedral coordination and the type II octants con-
with the atomic sphere approximation. tain aluminium ions in octahedral coordination. There are
However, to our knowledge, only a few theoretical and 96 interstices between the anions in the cubic unit cell;
experimental articles have been published on the optical however, in AB2O4 compounds, only 24 are occupied
properties of spinel MgAl2O4 oxide. Xu and Ching [12] by cations. Of the 64 tetrahedral interstices that exist be-
have studied the electronic structure, the charge density tween the anions, 8 are occupied by cations. The remaining
distribution and the optical absorption spectra of MgO, 16 cations occupy half of the 32 octahedral interstices. The
α-Al2O3 and MgAl2O4 crystal by the orthogonalized linear tetrahedrally coordinated cations form a diamond cubic
combination of atomic orbitals method. Thibaudeau and sublattice with a repeat unit equal to the lattice parameter.
Gervais [13] have performed ab initio calculations of infra- The periodicity associated with the sublattice of octahe-
red and Raman phonon modes in the normal cubic drally coordinated cations also is equal to the spinel lattice
MgAl2O4 spinel at the first Brillouin zone centre using parameter (a).
density functional theory (DFT) with plane-wave basis and
norm-conserving pseudopotentials. Bortz et al. [14] have 3 Method of calculation The calculations and re-
studied the room temperature optical reflectivity of MgO, laxation of the ionic positions were carried out with a self-
MgAl2O4 and α-Al2O3 from 5 eV to 40 eV using a novel consistent scheme by solving the Kohn–Sham equations
spectrophotometer with a laser plasma light source. using a FP-LAPW method in the framework of DFT along
In this paper the structure, band structure, total density with the generalized gradient approximation (GGA) [15,
of states and optical properties such as the dielectric func- 16] using Wien2k codes [17]. Since the calculation of
tion, reflectivity, refractive index and loss function of dielectric tensor requires a dense mesh of eigenvalues and
MgAl2O4 are calculated within the frame of the random the corresponding eigenvectors, the calculation of complex
phase approximation using DFT. dielectric tensor was performed with a fine k-mesh using
1000 k-point in the irreducible wedge of first Brillouin
2 Structure The structure of spinel is based on the zone. The values of other parameters are Rkmax = 7 (R is the
structure of diamond. The positions of the A ions are smallest muffin-tin radius and kmax is the cut-off for
nearly identical to the positions occupied by carbon atoms the plane wave) for the convergence parameter, Gmax = 14
in the diamond structure. This could explain the relatively (magnitude of largest vector in charge density Fourier ex-
high hardness and high density typical of this group. The pansion or the plane wave cut-off), and RMT(Mg) = 1.8 au,
arrangements of the other ions in the structure conform to RMT(Al) = 1.9 au and RMT(O) = 1.75 au (muffin-tin radii).

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2802 S. M. Hosseini: Properties of spinel MgAl2O4 oxide

The iteration halted when the charge difference was less 3.1.3 Optical properties The band-to-band transi-
than 0.0001e between steps as convergence criterion. The tion of an electron from the valence to conduction band is
cut-off energy, which defines the separation of valence and induced by incident light. The photon energy absorbed in
core states, was chosen as −6 Ry. the material per unit time and unit volume is equivalent to
the power dissipation of electromagnetic wave per unit
3.1 Structure optimization time and unit volume and thus is related to the imaginary
3.1.1 Lattice parameters From the literature, we part of the dielectric tensor via the equation [20]
know that the bulk elastic properties of a material deter-
pe 2
mine how much it will compress under a given amount of
external pressure. The ratio of the change in pressure to the
Im ε (ω ) =
ε 0 m 2ω 2
Âc ,v
2
e ◊ pcv d[ε ck - ε vk ¢ - ω ] δ kk ¢ (5)

fractional volume compression is called the bulk modulus

(B) of the material and can be written as where e ⋅ pcv is the matrix element for a transition from a
filled valence state of wave vector k′ to an empty conduc-
∂P tion state of wave vector k.
B = -V . (1)
∂V The dielectric function of an anisotropic material is a
complex symmetric tensor. In the limit of linear optics, in
In terms of energy, the bulk modulus is also defined by the
the case of non-spin polarization, and within the independ-
equation of state (EOS) and evaluated at the minimum as
ent particle approximation, random phase approximation
∂2 E (RPA), the imaginary part of the dielectric tensor can be
B =V . (2) computed from knowledge of the electronic band structure
∂V 2
of a solid from the well-known relation [21]
The position of the minimum of the EOS defines the equi-
4p e 2
librium lattice parameter and unit cell volume at zero pres-
sure. The static lattice potential corresponding to total en-
Im εαβ (ω ) =
m 2ω 2
Â Ú dk
c ,v
ck pα vk vk p β ck
ergy was calculated from a series of strained lattices. From ¥ d(ε ck - ε vk - ω ]) (6)
such results the equilibrium volume, bulk modulus and its
pressure derivative were derived. A series of total energy where vk and ck are electron states in the valence and
calculations as a function of volume can be fitted to an the conduction bands, respectively, with wave vector k.
EOS according to Murnaghan [18]: The real part of the frequency-dependent dielectric func-
B0V È (V0 /V ) B0¢ ˘ BV tion εαβ(ω) is given by
E (V ) = E0 + + 1˙ - 0 0 (3)
B0¢ ÍÎ B0¢ ˚ B0¢ - 1 2
•
ω ¢ Im εαβ (ω ¢)
p Ú0
Re εαβ (ω ) = δ αβ + P dω ¢ , (7)
where B0 is an equilibrium bulk modulus that effectively ω ¢2 - ω 2
measures the curvature of the energy versus volume curve
about the relaxed volume V0, and B′0 is the derivative of the which is named after Ralph Kronig and Hendrik Anthony
bulk modulus. Kramers, and where P is the Cauchy principal value.
The Kramers–Kronig relations allow calculation of the
3.1.2 Atomic relaxation Most structures have free refractive index and other optical constant profiles from
internal structural parameters, which can either be taken the frequency-dependent losses, which can be calculated
from experiment or optimized using the calculated forces over a large spectral range. The refractive index, n(ω), and
on the nuclei. Almost all optimization codes use what is the extinction coefficient, k(ω), are given by [22]

nαβ (ω ) = { 12 [ εαβ (ω ) + Re εαβ (ω )]}

called a quadratic approximation; they expand the energy 1/ 2
(8)
in the form
E* = E + g T s + ( 12 ) s T Hs (4) and

kαβ (ω ) = { 12 [ εαβ (ω ) - Re εαβ (ω )]}

1/ 2
where E* is the predicted energy for a step s from the cur- . (9)
rent point, E and g are the energy and gradient (negative of
At low frequency the static refractive index nαβ(0) can be
the force) calculated at the current point and H is the Hes-
calculated using the following expression for nonmagnetic
sian matrix.
materials:
Different algorithms use different approaches to the
2
Hessian matrix. The most primitive is steepest descent, nαβ (0) = Re εαβ (•) (10)
which takes H as the unitary matrix so will take a step
along the direction of the force [19]. For atomic relaxation where εαβ(∞) is the high-frequency dielectric constant. The
of MgAl2O4, we used the reverse-communication trust dielectric tensor is symmetric with up to six independent
region quasi-Newton method from the Port library which components according to the symmetry of the crystal. For
seems to be stable, efficient and does not depend too much the spinel MgAl2O4 structure, the optical properties are iso-
on the user input as implemented in the Wien2k package. tropic, i.e. there is only one independent component (εxx).

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phys. stat. sol. (b) 245, No. 12 (2008) 2803

The calculations were performed using GGA with

the relaxed atomic positions. The overall band profiles
calculated in this work are consistent with other first-
principles calculation results reported previously [10, 11].
The scale of energy in all figures is in eV and the top of
the valence band is set to zero (Fermi level) on the
energy scale. The valence bands are separated by a 5.2 eV
direct gap at Γ-point from the conduction band states.
Experimentally, the optical reflectivity measurements re-
ported the minimum band gap of MgAl2O4 to be direct at
Γ with a value of 7.8 eV [14]. Our calculated band gap
is smaller than the experimental values. This discrepancy
mainly arises from the GGA, which is known to underes-
timate the energy band gap of insulators. There are two
indirect band gaps in the [111] and [101] directions, along
Γ–L and Γ–X, with values of 7.5 and 8.2 eV, respec-
Figure 2 Calculated total energies versus volume for spinel tively.
MgAl2O4 oxide. Figure 4 shows the calculated total density of states for
the MgAl2O4 spinel structure. The lower O 2s band splits
4 Results and discussion into two: a very sharp peak at −16.0 eV and a lower part
4.1 Electronic structure The calculations first were 2.0 eV wide with double peaks. The sharp structures in the
carried out applying the experimental data for lattice con- energy range −18.2 to −15.5 eV are mainly due to O 2s
stant a = 8.0898 Å [23] then, by minimizing the total en- states. The upper valence band is composed mostly of O 2p
ergy of the crystal to the volume, the theoretical lattice states and hybridized with Mg 3s and Al 3p orbitals. The
constant was obtained as a = 8.1745 Å. Figure 2 shows the conduction band has compounds from both Mg 3s and Al
calculated total GGA energy Etot as a function of crystal 3p states.
volume for the spinel MgAl2O4 oxide. The electron density of spinel MgAl2O4 oxide in the
We minimized the energy for atomic positions and de- (100) plane for two and three dimensions is plotted in
termined the equilibrium position of individual atoms. The Fig. 5. This plane does not contain any magnesium ions
final calculation was performed with the theoretical lattice and shows the oxygen ions (large circles) and aluminium
constant and relaxed structure. The results of a full relaxa- ions (small circles) which are arranged diagonally between
tion of anion positions in the Fd3m structure of MgAl2O4 each other.
are summarized in Table 1. In Fig. 6 the electron density in the (110) plane for two
and three dimensions is shown. This plane contains all
4.2 Electronic properties The calculated electronic three types of ions. Between two rows of magnesium ions
band structure for the spinel MgAl2O4 oxide along the high of this plane there is an empty channel with almost no or
symmetry directions is shown in Fig. 3. little charge.

Table 1 Calculated and experimental crystallographic data for spinel MgAl2O4 oxide with space group Fd3m.

Wyckoff position ionic positions (x, y, z)

perfect ccp anion experimental [23] theoretical [13] (LDA) theoretical (GGA)
arrangement uideal
3m
[2] (neutron powder diffraction) (this work)
Mg (8a) (1/8, 1/8, 1/8) (1/8, 1/8, 1/8) (1/8, 1/8, 1/8) (1/8, 1/8, 1/8)
Al (16d) (1/2, 1/2, 1/2) (1/2, 1/2, 1/2) (1/2, 1/2, 1/2) (1/2, 1/2, 1/2)
O (32e) (1/4, 1/4, 1/4) (0.261714, 0.261714, (0.2735, 0.2735, 0.2735) (0.2632, 0.2632, 0.2632)
0.261714)
experimental theoretical this work
lattice constant, a (Å) 8.08360 [23] 8.0832 [8], 8.027 [11], 8.1074
7.905 [13]
bulk modulus, B (GPa) 196 [24] 213 [9], 220 [11], 199 [13] 188.4
derivative of the bulk 4.89 [24] 5.40 [9], 2.95 [11], 3.66 [13] 4.4503
modulus, B′
bond lengths (Å):
Mg – O – 1.96 [8] 1.9569
Al – O – 1.82 [8] 1.9416

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2804 S. M. Hosseini: Properties of spinel MgAl2O4 oxide

Figure 4 Total density of states (DOS) of spinel MgAl2O4 struc-

ture and total Mg, Al and O atoms.

this is due to the fundamental gap. This peak is related to

a) the interband transition from the valence to the conduction
band states along Γ–Γ direction. For simplification of
analysis of the other optical transition spectra, the labels
E0, E1 and E2 have been used. The subscript 0 in E refers to
transition along [000] and 1 for transitions at points in
[111] direction and 2 for transitions in the [100] direction
of k space. These notations are used based on those of
Ref. [25] to describe the reflectivity spectra of semicon-
ductors of wurtzite and zinc blend structures. For the spinel
structure with space group Fd3m (number 227), the [111]
direction is along Γ–L and [100] is from Γ–X.
The most important contribution to the peaks E1 and E2
arises from the transitions from the uppermost valence
band to the first conduction band. The major contributions
to the intensity of these peaks are throughout the large vol-
ume of the Brillouin zone. The positions of five peaks in
the imaginary part of the dielectric function calculated in
this work are summarized in Table 2.
Figure 3 (online colour at: www.pss-b.com) a) Band structure
and b) the first Brillouin zone of spinel MgAl2O4 structure. Table 2 Peak values of the imaginary part for spinel MgAl2O4
oxide for transition from the uppermost valence to conduction
band.
4.3 Optical properties The real and imaginary parts
of the frequency-dependent dielectric function for the peak energy (eV) (this work) experimental
spinel MgAl2O4 structure are shown in Fig. 7. The static
dielectric permittivity tensor, εαβ(0), of a nonpolar material E0 (Γ → Γ) 6.27 7.8 [14]
contains electronic (high-frequency) and ionic contribu- E′0 (Γ → Γ) 9.42 11.0 [14]
tions. The high-frequency dielectric constant, ε(∞), of E1 (Γ → L) 7.44
spinel MgAl2O3 oxide is presented in Table 3. The cal- E′1 (Γ → L) 10.19
culated Im ε(ω) shows the first peak at about E0 = 6.27 eV; E2 (Γ → X) 8.61

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-b.com

 Original
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phys. stat. sol. (b) 245, No. 12 (2008) 2805

a) b)

Figure 5 (online colour at: www.pss-b.com) Electron densities of spinel MgAl2O4 oxide in the (100) plane in a) two and b) three
dimensions.

a) b)

Figure 6 (online colour at: www.pss-b.com) Electron densities of spinel MgAl2O4 oxide in the (110) plane in a) two and b) three
dimensions.

Figure 7 Calculated a) real and b) imaginary parts of the dielectric function for spinel MgAl2O4 oxide.

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2806 S. M. Hosseini: Properties of spinel MgAl2O4 oxide

Figure 8 a) Refractive index and b) reflectivity for spinel MgAl2O4 oxide.

In Fig. 8 the refractive index, n(ω), and the reflectivity, 4.3.2 Electron energy loss spectroscopy Plasmon
R(ω), are shown for spinel MgAl2O4 structure. The mate- losses correspond to a collective oscillation of the valence
rial is transparent in the visible and the excitonic transition electrons and their energy is related to the density of
associated with the fundamental absorption edge increases valence electrons. In the case of interband transitions,
in the series from 6.27 eV to 10.19 eV. At phonon energies which consist mostly of plasmon excitations, the scattering
above 24.5 eV the reflectivity magnitudes begin to de- probability for volume losses is directly connected to
crease and the interband transitions are exhausted by 40 eV. the energy loss function. One can then calculate the elec-
The experimental spectrum of reflectivity of MgAl2O4 tron energy loss spectrum from the following relations
from 5 to 40 eV using a novel spectrophotometer with a [21]:
laser plasma light source is also plotted in Fig. 8 [14]. εαβ (ω ) = ε1 + iε 2
In order to obtain an accurate value of static dielectric
constant, we should add to the electronic part the optical and
phonon contribution. However, in this calculation we did È -1 ˘ ε2
not include such a contribution and the values of high fre- Lαβ (ω ) = Im Í ˙= 2 2
. (11)
quency dielectric constant have been evaluated at nearly Î ωαβ (ω ) ˚ ε1 + ε 2
zero value of energy. The refractive index is then obtained In Fig. 10 the energy loss function is plotted for spinel
from Eq. (10) as n(0) ≈ 1.763 which is close to the experi- MgAl2O4 oxide. There are other peaks and features in this
mental value of 1.71 [26]. The static refractive index is spectrum, in addition to the plasmon peak, associated with
summarized in Table 3. interband transitions. The plasmon peak is usually the most
intense feature in the spectrum and this is at an energy
4.3.1 Dispersion of the refractive index The dis- where Re ε(ω) goes to zero, after the zero-loss peak; the
persion curve of the refractive index is shown in Fig. 9.
The curve is fairly flat in the long-wavelength region
and rises rapidly towards shorter wavelengths, showing the
typical shape of a dispersion curve near an electronic inter-
band transition.
The strong increase in the refractive index is associated
with the fundamental band gap absorption. The refractive
index is 1.774 at 800 nm near the visible region; the wave-
lengths of visible light are shaded.

Table 3 Refractive indices and high-frequency dielectric con-

stants for spinel MgAl2O4 oxide.

method n(0) ε (∞)

experimental:
bulk 1.712 – 1.762 [26] 2.89 [28]
thin film 1.69 – 1.73 [27]
theoretical 1.7320 [13] 3.00 [13]
Figure 9 Wavelength dispersion curve of the refractive index for
theoretical (this work) 1.763 3.112
spinel MgAl2O4 oxide.

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phys. stat. sol. (b) 245, No. 12 (2008) 2807

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