Chemical Physics Letters 637 (2015) 172176

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Chemical Physics Letters

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

Elucidating the high-k insulator -Al2 O3 direct/indirect energy band

gap type through density functional theory computations
R.C.R. Santos a , E. Longhinotti a , V.N. Freire b , R.B. Reimberg c , E.W.S. Caetano c,
a
Departamento de Qumica Analtica e Fsico-Qumica, Universidade Federal do Cear, 60455-900 Fortaleza, CE, Brazil
b
Departamento de Fsica, Universidade Federal do Cear, Centro de Cincias, Caixa Postal 6030, Campus do Pici, 60455-760 Fortaleza, CE, Brazil
c
Instituto Federal de Educaco, Cincia e Tecnologia do Cear, Programa de Ps-Graduaco em Engenharia de Telecomunicaces, 60040-531 Fortaleza,
CE, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The measured band gap of the high-k insulator -Al2 O3 is direct (8.80 eV) but previous theoretical esti-
Received 8 July 2015 mates were not conclusive regarding its direct/indirect character. Thus, we have performed density
In nal form 3 August 2015 functional theory (DFT) computations of the structural and electronic properties of -Al2 O3 employ-
Available online 12 August 2015
ing several exchange-correlation functionals and the -sol scheme. Among the functionals tested, the
best results were obtained for the sX-LDA calculation, which predicted an indirect gap of 8.826 eV. The
lattice parameter dependence of the -Al2 O3 gap type, on the other hand, suggests a subtle transition for
temperatures above 400 K due to thermal expansion.
2015 Elsevier B.V. All rights reserved.

The aggressive scaling of gate length and equivalent gate oxide
thickness demanded by the International Technology Roadmap for
Semiconductors [1] have turned aluminum oxide -Al2 O3 (sap-
phire or corundum) into an interesting material to replace standard
SiO2 technologies. It has an experimental wide direct band gap of
8.8 [26] and a 2.8 eV conduction band offset (similar to SiO2 ) [7,8].
Efforts to increase its modest dielectric constant ( 9.0) by appro-
priate doping are being undertaken [9]. Among its applications,
-Al2 O3 is used as a substrate for the growth of silicon and gal-
lium nitride, and as an active medium in lasers when doped with
chromium or titanium. A detailed description of the -Al2 O3 crystal
structure was given by Batra [10]: its primitive unit cell is rhombo-
hedral (space group R-3C), containing two Al2 O3 units, but it can
also be described using a hexagonal unit cell [11,12] with lattice
parameters a = 4.756 Aand c = 12.982 A[13] at 4.5 K and containing
12 six-coordinated Al atoms and 18 four-coordinated O atoms.
Barrier height (associated to the gap energy and band offset) and
charge carrier effective masses are key parameters to model the
tunneling mechanism which describes charge injection through a
perfect dielectric layer, being estimated through electronic band
structure calculations. In the case of -Al2 O3 , the pioneer calcula-
tions for the crystal were non-self-consistent or semiempirical in
nature, but some were developed for small clusters, as reviewed
briey by Xu and Chin [14]. The rst -Al2 O3 self-consistent band
Corresponding author at: Instituto Federal de Educaco, Cincia e Tecnologia do
Cear, Av. 13 de Maio, 2081, Benca, 60040-531 Fortaleza, Cear, Brazil.
structure was obtained in a preliminary way by French [15], soon
followed by the landmark work of Xu and Chin [14] (see also [16])
in which the rst-principles orthogonalized linear combination of
atomic orbitals method (OLCAO) in the local density approximation
(LDA) within the density functional formalism (DFT) was used. They
have obtained an indirect band gap of 6.29 eV involving a transition
from the top of the valence band at a point at 20% of the X line
and the bottom of the conduction band at  [14]; effective masses
obtained for the electrons were 0.16 along the  X direction, 0.45
along  Z, 0.40 along  A and 0.38 along  D (values given in
units of the free electron mass, mo ), while the hole effective masses
were not evaluated due to the atness of the valence band [14]. The-
oretical DFT works on the -Al2 O3 electronic structure published
afterwards have obtained similar estimates for the gap energy (all of
them, however, with direct main gaps) and carrier effective masses
[5,6,1721]. Samantaray et al. have found a direct band gap of 6.1 eV
for -Al2 O3 at the  point [4] using the LDA exchange-correlation
potential, while Mousavi et al. [22], using the Full Potential Lin-
earized Augmented Plane Wave (FP-LAPW) approach employing
the EngleVosko approximation (EVA) have found a direct band
gap of 7.2 eV. The electronic structure calculated for a thin lm of
-Al2 O3 , by the way, has revealed a band gap of only 2.6 eV [23],
much smaller than the bulk. The electronic structure of amorphous
alumina was investigated using classical molecular dynamics and
X exchange potentials [24], being shown a local oxygen deciency
around Al atoms. On the other hand, GW calculations performed by
Marinopoulos and Grning predict a direct band gap of 9.36 eV for
-alumina [25], while another study by Choi et al. [26], using the

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 R.C.R. Santos et al. / Chemical Physics Letters 637 (2015) 172176 173

hybrid HSE exchange-correlation functional, predicted a band gap

of 9.2 eV. A calculated B3LYP band gap of 8.5 eV for -Al2 O3 , in con-
trast, was obtained by Muscat et al. [27], while a mBJ band gap of
approximately 9.0 eV was found by Lima et al. [9].
In this Letter, we have performed a series of simulations within
the density functional theory formalism to improve the under-
standing of the nature of the -Al2 O3 main energy band gap. At
room temperature, all experimental data available indicate that
this material has a wide direct band gap, and all theoretical studies
agree that the top of the valence band of -Al2 O3 is very at. Such
valence band atness seems to imply that the exact nature of the
band gap of alumina is strongly sensitive to variations in its lat-
tice parameters. As a matter of fact, some theoretical reports have
found an indirect band gap [14,16,15] for -Al2 O3 .
The computations we carried out used as initial structure
the unit cell lattice parameters at 4.5 K for alumina found in
Ref. [13], which employed the Mssbauer wavelength standard
to achieve very precise measurements. Geometry optimizations
were performed taking into account four parametrizations for the
exchange-correlation functional: the local density approximation
(LDA) model of Ceperley and Alder [28], and the generalized gra-
dient approximation (GGA) models of PerdewBurkeErnzerhof
[29] (PBE), the revised PBE model (RPBE [30]), and the PBESOL
model [31] (optimization for the solid state). As it is known, the
KohnSham band gaps obtained from pure DFT calculations are
usually well below experimental values [32]. In order to address
Figure 1. Hexagonal (top) and rhombohedral (bottom) unit cell representations of
this issue, single point energy calculations were worked out for
-Al2 O3 are shown at the left side, while the corresponding rst Brillouin zones
the optimized structures using the hybrid functionals PBE0 [33] are shown at the right side. High symmetry points and reciprocal lattice axis are
(PBE optimized geometry), HSE06 [34] (PBESOL optimized unit depicted as well.
cell), and B3LYP [35] (PBESOL optimized unit cell) in order to
improve the band gap estimate (hybrid functional simulations, xed. The self-consistent eld energy convergence tolerance was
while computationally much more expensive than pure DFT imple- set to 5.0 107 eV/atom with a convergence window of three iter-
mentations, predict much better band gaps, comparable to those ations. The pure DFT calculations were carried out using the larger
obtained using more sophisticated methods such as the QMC hexagonal unit cell of alumina, while the hybrid, sX-LDA calcula-
and GW approaches [27]). We have also employed the screened tions were performed using the smaller rhombohedral unit cell to
exchange LDA scheme (sX-LDA [32]) to estimate more accurately decrease the computational cost (both cells and the corresponding
the band gap of the LDA-optimized geometry. In the sX-LDA rst Brillouin zones are shown in Figure 1).
method, the exchange contribution to the total energy is splitted The lattice parameters resulting from the DFT geometry opti-
into two parts: a screened, nonlocal and a local density com- mization procedures are shown in Table 1, where both the
ponent. Lastly, we have also applied the -sol technique [36] hexagonal and rhombohedral unit cell data are presented. For the
to obtain gap estimates directly from the pure DFT exchange- hexagonal structure, the ah (ch ) LDA lattice parameter is 0.98%
correlation functionals. Overall, we have found a total of 12 band (1.0%) smaller than the experimental value, while the volume Vh is
gap estimates to be discussed and compared with the experimental 3.0% smaller. This is not surprising, as the LDA exchange-correlation
value. energy tends to overestimate the strength of the atomic binding.
In order to perform all the calculations, the plane-wave basis The GGA results, on the other hand, exhibit lattice parameters larger
set CASTEP code [37] was used together with on the y generated than the measured ones (GGA functionals in general underesti-
ultrasoft pseudopotentials (applied for the geometry optimiza- mates the binding strength in solids), with the worst gures being
tions and electronic band structure computations in the LDA and obtained for the RPBE unit cell: 1.3% larger for ah and 1.4% larger for
GGA frameworks) and norm-conserving pseudopotentials (applied ch . In the PBE case, ah and ch are, respectively, 0.59% and 0.66% larger
when using hybrid functionals and the LDA screened exchange than the X-ray data. Indeed, the best agreement with the experi-
approach) for the description of the core electrons, with valence mental parameters is found for the PBESOL converged unit cell, with
electronic congurations for the oxygen and aluminium atoms the theoretical values ah and ch being only 0.11% and 0.15% smaller,
being 2s2 2p2 and 3s2 3p1 , in this order. A MonkhorstPack 3 3 2 respectively (in this case, the PBESOL seems to slightly overesti-
(4 4 4) grid was adopted to evaluate integrals in reciprocal mate the binding of the atoms, against typical GGA behaviour).
space for the hexagonal (rhombohedral) -Al2 O3 unit cell, while
the plane wave cutoff energy was set to 610 eV (750 eV) when Table 1
using the ultrasoft (norm-conserving) pseudopotentials, ensur- Calculated lattice parameters for -Al2 O3 using different DFT exchange-correlation
ing a very good quality for the electronic structure it is about functionals versus experiment. Hexagonal (h subscript) and rhombohedral (r sub-
twice the cutoff energy values used in the previous works on the script) unit cell data are shown. V is the unit cell volume.
DFT-calculated -Al2 O3 structural and electronic properties. The LDA PBE RPBE PBESOL EXP [13]
geometry optimization convergence thresholds were: energy vari-
ah (A) 4.70950 4.78447 4.81762 4.75095 4.75630
ation smaller than 5.0 106 eV/atom, maximum force smaller ch (A) 12.8458 13.0684 13.1692 12.9626 12.9820
than 0.01 eV/A, maximum stress smaller than 0.02 GPa and max- Vh (A3 ) 246.740 259.072 264.701 253.387 254.338
imum atomic displacement smaller than 5.0 104 A. Both the ar (A) 5.07227 5.15812 5.19676 5.11799 5.12510
internal atomic coordinates and the unit cell lattice parameters (deg) 55.3220 55.2626 55.2292 55.3094 55.2937
Vr (A3 ) 82.2466 86.3573 88.2337 84.4624 84.7792
were relaxed, with quality of the plane wave basis set being kept
174 R.C.R. Santos et al. / Chemical Physics Letters 637 (2015) 172176

Figure 2. Close-up of the GGA-PBE KohnSham band structure (left) and respective partial density of states (right) near the main band gap of -Al2 O3 (hexagonal unit cell).

The angle for the rhombohedral unit cell, in contrast, is over-
estimated by both the LDA (0.05%) and PBESOL (0.03%) approaches,
and underestimated when using the PBE (0.06%) and RPBE (0.1%)
exchange-correlation energies.
In Figure 2, we have a close-up of the KohnSham band structure
near the main band gap of -Al2 O3 for the hexagonal unit cell. One
can see that the uppermost valence band has its maximum at the 
point with very small dispersion except along the A line, which
means a large and anisotropic hole effective mass for this material.
The valence band electronic states are mainly originated from O
2p orbitals, with very small contributions from Al 3p and 3s states.
The bottom of the conduction band, on the other hand, has a much
larger curvature, with a nearly parabolic minimum at the  point,
indicating an almost isotropic electron effective mass. These results
are in nice agreement with the paper published by Perevalov et al.
[6], which have predicted a perpendicular hole effective mass of 6.3
(in units of the free electron mass) and an isotropic electron effec-
tive mass of approximately 0.4 using the GGA-PBE functional. The
GGA-PBE band gap we obtained was 6.045 eV, a value a bit smaller
than the value found in Perevalovs study (6.26 eV), probably due to
pseudopotential differences. The conduction band minimum has a
very small density of states (about 1 electron/eV), with dominant
contribution from Al 3s states, followed by O 2s and a very tiny
amount of Al 3p character. A secondary conduction band at the
A point with energy 6.7 eV has a much larger DOS (about 6 elec-
trons/eV), with strong Al 3s contribution. Above 8.5 eV, the PDOS
originates mainly from Al 3p and O 2p orbitals.
As we switch from one exchange-correlation functional to
another, the band gap changes, as shown in Table 2. In all cases,
except for the sX-LDA calculation, the -Al2 O3 crystal has a direct
gap at the  point. The RPBE and PBESOL computations predict
the same gap value, of 5.881 eV, while the LDA result is 6.594 eV.
For the hybrid functionals, the closest match to experiment was
found for B3LYP, 8.674 eV (even better than the previous calcula-
tion by Muscat et al. [27], which have obtained 8.5 eV), followed
by PBE0 (8.554 eV), and HSE06 (8.088 eV, about 1 eV smaller than
the HSE estimate of Choi et al. [26]). The screened exchange LDA
approach, in contrast, predicts an indirect gap which is very close to
the experimental data, 8.826 eV, with the maximum of the valence
band along the F line. The  gap, by the way, is just 9 meV
bigger.
The -sol scheme is a generalization to the solid state of the
 self-consistent eld approach used in molecular systems, being
based on the variation of unit cell total energies with the unit

Figure 3. Left: PBE and PBE0 band structures near the main band gap of -Al2 O3 (rhombohedral unit cell). Right: the same for the LDA and sX-LDA band structures.
 R.C.R. Santos et al. / Chemical Physics Letters 637 (2015) 172176 175

Table 2
Calculated energy band gaps for -Al2 O3 using different DFT exchange-correlation
functionals in comparison with the experimental data. Gap types (d: direct/i: indi-
rect) are also shown.

Eg -sol Eg (eV) Transition

(eV) (eV)

LDA (d) 6.594 8.530 

PBE (d) 6.045 7.885 
RPBE (d) 5.881 7.703 
PBESOL (d) 5.881 8.065 
sX-LDA (i) 8.826 - F 
sX-LDA (d) 8.835 - 
PBE0 (d) 8.554 - 
HSE06 (d) 8.088 - 
B3LYP (d) 8.674 - 
EXP (d) [2,3,6] 8.8 - 

cell charge [36]. Its main advantage is the much smaller computa-
tional cost in comparison with hybrid functional calculations and
other more advanced techniques for band gap correction. The -sol
corrected gaps for the PBE exchange-correlation family of func-
tionals are, in increasing order, 7.703 eV (RPBE), 7.885 eV (PBE),
and 8.065 (PBESOL) eV (see Table 2). For the LDA, this method
improves the gap to 8.530 eV, just about 0.3 eV below the measured
gap.
From the top (bottom) of Figure 3, one can perform a com-
parison between the PBE and PBE0 (LDA and sX-LDA) electronic
band structures in the rst Brillouin zone for the rhombohedral
unit cell of alumina. For the valence band, one can see that the
PBE0 hybrid functional shifts the band curves to lower energies
relative to the PBE data, while the conduction bands are energeti-
cally shifted upwards. The shapes of the band curves, however, do Figure 4. Unit cell total energy (top) and main band gap (bottom) of -Al2 O3 as a
not change signicantly. The same can be said for the comparison function of the lattice parameter ratio  = a/a0 = b/b0 . Black (red) squares and circles
between the LDA and sX-LDA outputs, with the difference that the indicate that the main band gap for the corresponding  is direct (indirect). (For
sX-LDA valence band curves tend to be shifted to higher energy interpretation of reference to color in this gure legend, the readers is referred to
the web version of this article.)
values relative to the corresponding LDA bands.
Aiming to investigate the dependence of the nature of the
band gap with the unit cell lattice parameters, we have performed see the valence band maximum at  and a small shoulder at approx-
a series of calculations using the LDA and GGA-PBE functionals imately one third of the k line. For  = 1.010 (an increase of 1% in
starting from the previously optimized structures. We started by the lattice parameters), the shoulder turns into a secondary maxi-
dening a lattice parameter ratio  = a/a0 = c/c0 for the hexago- mum just 1 meV below the main maximum at , and for  = 1.015,
nal unit cell, where a0 and c0 are the optimized values shown in the indirect gap is greater than the direct value by about 6 meV.
Table 1. This  parameter was varied from 0.9 to 1.1 (shrinking Finally, for  = 1.020, the indirect gap is 12 meV above the direct
or enlarging the crystal, as > or <1, respectively) and the inter- gap at the  point. The valence band curves below the uppermost
nal atomic coordinates were relaxed for each unit cell volume thus
obtained. We have plotted the unit cell total energy and the main
energy band gap as a function of  at the top and bottom parts of
Figure 4. From it, one can see that the LDA total energy is larger
than the GGA-PBE value for a given , with both displaying a nearly
parabolic shape. The main energy band gap Eg , on the other hand,
decreases almost linearly with  as it increases from 0.9 to 1.1. For
the LDA gap curve, Eg decreases from 10.435 eV ( = 0.9) to 3.285 eV
( = 1.1), with an average rate of decrease of 3.575 eV per 0.1 ,
while for the GGA-PBE case we have a maximum gap of 10.325 eV
( = 0.9) and a minimum of 2.857 eV ( = 1.1), with average rate
of decrease 3.734 eV per 0.1 . One can note, for the LDA Eg ()
curve, that the rst point, corresponding to  = 0.9, has an energy
gap a bit smaller than the expected from linear extrapolation. It is
also distinct due to the fact that its minimum band gap is indirect,
with the valence band maximum at the  point and the conduc-
tion band minimum at M. Indeed, for both LDA and GGA-PBE band
gap curves, one can see that a slight increase of at least 2% in the
lattice parameter sufces to turn alumina into an indirect gap insu-
lator (see red circles and squares at the right side of each plot in
Figure 4). Figure 5. Top of the GGA-PBE valence band of alumina for distinct values of the
Figure 5 details the direct-indirect gap transition for unit cell lattice parameter ratio  revealing a direct to indirect gap transition (the bottom of
optimized employing the GGA-PBE functional. At  = 1.000 one can the conduction band, not shown here, is at the  point for all  values).
176 R.C.R. Santos et al. / Chemical Physics Letters 637 (2015) 172176
valence band are energetically shifted upwards by the increase of
. If one considers the results of the measurements carried out by
Lucht et al. [13] of the lattice parameters of -Al2 O3 as a function of
temperature, it is expected an increase of more than 1.5% percent of
A and b (using the T = 4.5 K data as reference) when the temperature
is close to 400 K, so one must hope to observe the directindirect
transition of aluminas main band gap as the temperature increases
to nearly that value.
In summary, we have presented the result of a series of DFT cal-
culations to estimate more accurately the main bad gap of -Al2 O3
and to elucidate its character (direct or indirect) as a function of
the unit cell lattice parameter. After geometry optimization, the
PBESOL exchange-correlation functional has predicted the best lat-
tice parameters in comparison with precise X-ray diffraction data
for alumina at T = 4.5 K. For the band gap, the most accurate results
versus the experimental gap Eg = 8.8 eV were obtained by using
the screened-exchange LDA approach, which predicted an indirect
band gap of 8.826 eV and a very close direct gap of 8.835 eV, fol-
lowed by the B3LYP hybrid functional, with Eg = 8.674 eV (direct).
The PBE0 gap was 8.554 eV, while the HSE06 functional had the
worst gure among the hybrid functionals, 8.088 eV. -sol cor-
rected gaps were also calculated, with the LDA--sol corrected gap
reaching 8.53 eV, as good as the PBE0 value, notwithstanding the
much cheaper computational cost of this approach. Direct to indi-
rect gap transitions were observed for unit cells optimized using
both the LDA and GGA-PBE functionals as the unit cell parame-
ters are increased, with a directindirect transition being found in
the GGA-PBE case for an (a, c) increase of just 1.5% relative to the
optimized lattice parameters. This suggests that a subtle gap type
transition as a function of temperature must occur for T 400 K
as the lattice parameters of the crystal increase due to thermal
expansion.
Acknowledgments
V.N.F. is a senior researcher from the Brazilian National Research
Council (CNPq). E. W. S. C. received nancial support from CNPq
project 307843/2013-0.
References
[1] International Technology Roadmap for Semiconductors: 2012 update review,
Semiconductor Industry Association, San Josa, CA, http://public.itrs.net/
[2] M.L. Bortz, R.H. French, Appl. Phys. Lett. 55 (1989) 1955.
[3] M.E. Innocenzi, R.T. Swimm, M. Bass, R.H. French, A.B. Villaverde, M.R. Kokta, J.
Appl. Phys. 67 (1990) 7542.
[4] C.B. Samantaray, H. Sim, H. Hwang, Appl. Surf. Sci. 242 (2005) 121.
[5] S.M. Hosseini, H.A.R. Aliabad, A. Kompany, Eur. Phys. J. B. 43 (2005) 439.
[6] T.V. Perevalov, A.V. Shaposhnikov, V.A. Gritsenko, H. Wong, J.H. Han, C.W. Kim,
JETP Lett. 85 (2007) 165.
[7] R. Ludeke, M.T. Cuberes, E. Cartier, Appl. Phys. Lett. 76 (2000) 2886.
[8] J. Robertson, Eur. Phys. J. Appl. Phys. 28 (2004) 265.
[9] A.F. Lima, J.M. Dantas, M.V. Valic, J. Appl. Phys. 112 (2012) 093709.
[10] I.P. Batra, J. Phys. C 18 (1982) 5399.
[11] F.S. Galasso, Structure and Properties of Inorganic Solids, Pergamon, New York,
1970.
[12] ICSD 2003 Collection, Entry # 88029.
[13] M. Lucht, M. Lerche, H.-C. Wille, Y.V. Shvydko, H.D. Rter, E. Gerdau, P. Becker,
J. Appl. Cryst. 36 (2003) 1075.
[14] Y.-N. Xu, W.Y. Ching, Phys. Rev. B 43 (1991) 4461.
[15] R.H. French, J. Am. Ceram. Soc. 73 (1990) 477.
[16] W.Y. Ching, Y.-N. Xu, J. Am. Ceram. Soc. 77 (1994) 404.
[17] P.W. Peacock, J. Robertson, J. Appl. Phys. 92 (2002) 4712.
[18] W.Y. Ching, L. Ouyang, P. Rulis, H. Yao, Phys. Rev. B 78 (2008) 014106.
[19] H.A.R. Aliabad, M.R. Benam, H. Arabshahi, Int. J. Phys. Sci. 4 (2009) 437.
[20] T.V. Perevalov, V.A. Gritsenko, Physics Uspekhi 53 (2010) 561.
[21] T.V. Perevalov, V.A. Gritsenko, V.V. Kaichev, Eur. Phys. J. Appl. Phys. 52 (2010)
30501.
[22] S.J. Mousavi, M.R. Abolhassani, S.M. Hosseini, S.A. Sebt, Chin. J. Phys. 47 (2009)
862.
[23] K. Shiiki, M. Igarashi, H. Kaijyu, Jpn. J. Appl. Phys. 42 (2003) 5185.
[24] H. Chang, Y. Choi, K. Kong, B.-H. Ryu, Chem. Phys. Lett. 391 (2004) 293.
[25] A.G. Marinopoulos, M. Grning, Phys. Rev. B 83 (2011) 195129.
[26] M. Choi, A. Janotti, C.G. Van de Walle, J. Appl. Phys. 113 (2013) 044501.
[27] J. Muscat, A. Wander, N.M. Harrison, Chem. Phys. Lett. 342 (2001) 397.
[28] D.M. Ceperley, B.J. Alder, Phys. Rev. Lett. 45 (1980) 566.
[29] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.
[30] B. Hammer, L.B. Hansen, J.K. Norskov, Phys. Rev. B 59 (1999) 7413.
[31] J.P. Perdew, A. Ruzsinszky, G.I. Csonka, O.A. Vydrov, G.E. Scuseria, L.A. Con-
stantin, X. Zhou, K. Burke, Phys. Rev. Lett. 100 (2008) 136406.
[32] A. Seidl, A. Grling, P. Vogl, J.A. Majewski, M. Levy, Phys. Rev. B 53 (1996) 3764.
[33] C. Adamo, V. Barony, J. Chem. Phys. 110 (1998) 6158.
[34] A.V. Krukau, O.A. Vydrov, A.F. Izmaylov, G.E. Scuseria, J. Chem. Phys. 125 (2006)
224106.
[35] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[36] M.K.Y. Chan, G. Ceder, Phys. Rev. Lett. 105 (2010) 196403.
[37] S.J. Clark, M.D. Segall, C.J. Pickard, P.J. Hasnip, M.J. Probert, K. Refson, M.C. Payne,
Z. Kristall. 220 (2005) 567.