Journal of Molecular Structure: THEOCHEM 723 (2005) 135–138

www.elsevier.com/locate/theochem

Ab initio calculations of electronic properties of pure

and Ge doped anatase TiO2
Qiang Chen*, Hong-Hong Cao
School of Science, Beijing University of Aeronautics and Astronautics, 37 Xue Yuan Road, Haidian District, 100083 Beijing, People’s Republic of China
Received 18 May 2004; accepted 1 October 2004
Available online 5 April 2005

Abstract
In this paper we compared the electronic properties of the Ge doped anatase TiO2 with that of the pure host lattice. The ab initio
calculations were performed by using the full potential-linearized augmented plane wave method (FP-LAPW). The fully optimized structure
and the relaxation introduced by the impurity were obtained by minimizing the total energy and atomic forces. The resulted band structure,
density of states maybe instructive to the understanding of exceptional behavior in this system.
q 2004 Elsevier B.V. All rights reserved.

Keywords: Ab initio; DFT; FP-LAPW; Anatase; TiO2; Electronic properties

1. Introduction The results include the fully optimized ground-state

Titanium dioxide (TiO2) has received intensive attention
as a promising material for photochemical applications and
as a photocatalyst because of its excellent functionality,
long-term stability, and non-toxity [1]. Rutile, anatase, and
brookite are the three distinct polymorphs of TiO2. Anatase
is less stable than rutile, but is more efficient and more
widely used in catalysis and photoelectrochemistry. TiO2 is
a wide-gap semiconductor: the band gap energy of anatase
is 3.2 eV, which means that it is mainly activated by
ultraviolet (UV) lights. Many studies [2–8] such as cation-
doped TiO2 have been carried out in the attempt to shifted
the absorption edge to a lower energy, thereby increasing
the photoreactivity in the visible-light region. Recently,
Fromknecht [9,10], etc. reported experimentally the excep-
tional behavior of Ge- and Pb-implanted TiO2 single
crystals in diffusion effects and conductivity. In this paper
we investigated the electronic structure of the Ge doped
anatase TiO2, which should be helpful to understand some
of the experimental results.
This paper presents the ab initio calculations of TiO2
in the anatase structure using FP-LAPW method.
* Corresponding author.
E-mail address: qchen@buaa.edu.cn (Q. Chen).
0166-1280/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2004.10.008
structure obtained with total energy and atomic forces,
band structure, charge densities and densities of states.
The article is organized as follows: the computing model
systems and methods are described in Section 2, the
results are reported and discussed in Section 3, a short
section of conclusions closes the paper.
2. Calculation models and methods
Anatase is one of the two most common and widely used
polymorphs of TiO2. Its structure can be described in terms
of chains of TiO6 octahedra. In the anatase structure each
octahedron is in contact with eight neighbors (four sharing
an edge and four sharing a corner) [11]. The conventional
unit cell of TiO2 in the doped anatase structure is shown in
Fig. 1, which the doped Ge atom replace the Ti at the center
of unit cell. Besides, two lattice parameters, a, c, the
parameter dap is the apical Ti–O or Ge–O bond length, deq is
the equatorial bond length correspondingly [12].
The atomic configuration of titanium is [Ar] 3d2, 4s2 and
that of germanium is [Ar] 3d10, 4s2, 4p4 while for oxygen it
is [He] 2s2, 2p4. In many cases it is desirable to distinguish
three types of electronic states, namely core, semi-core
and valence states. In our work we treat the Ti 1s, 2s and 2p
136 Q. Chen, H.-H. Cao / Journal of Molecular Structure: THEOCHEM 723 (2005) 135–138

impurity replaces a Ti atom and the electronic structure of

the resulting system. The FP-LAPW method that we
employed, for reliability, treats all electrons and has no
shape approximations for the potential and charge density
[17]. The implementation of the FP-LAPW method includes
total energy [18] and atomic-force calculations [19], which
allow structure optimization [20]. The optimized structure
of pure anatase and the relaxed structure of the doped for a
set of V and c/a were decided when the total energy was
minimized and the force on each atom was smaller than
1 mRy/a.u. All results in this work were obtained under
these conditions.

Fig. 1. The conventional unit cell of anatase TiO2. Dark gray and white
balls correspond to oxygen and titanium atoms, respectively, assuming that
Ge (black) replaces Ti atom at the center of unit cell (for interpretation of
the references to colour in this figure legend, the reader is referred to the
web version of this article).
states, Ge 1s, 2s, 2p, 3s, 3p together with the O 1s as core
states. The semi-core states are Ti 3s, 3p, O 2s and Ge 3d,
which correspond to local orbitals (LO). This leaves the Ti
3d, 4s, O 2p and Ge 4s, 4p as valence states, respectively.
The calculations were carried out by using FP-LAPW
method within density-functional theory (DFT) [13–15].
We worked in generalized gradient approximation (GGA)
[16]. In this method, the unit cell is divided into two
regions: non-overlapping atomic spheres with radii and an
interstitial region. Taking the structure optimization into
account, the atomic sphere radii adopted for Ti, O and Ge
were 0.95, 0.79 and 1.06 Å, respectively. We took for the
parameter RKMAX the value of 7. The basis sets consist
of 2978 LAPW functions. We also introduced local orbitals
(LO) to include Ti 3s, 3p, O 2s and Ge 3d orbitals.
Integration in a reciprocal space was performed by the
tetrahedron method taking 84 k-points in the irreducible
Brillouin zone (IBZ). The calculation was carried out self-
consistently and stopped by the force convergence criterion.
Our aim is to calculate from first principles the structural
relaxations produced in the anatase TiO2 when a Ge
3. Results and discussion
To calculate the optimized structure of the pure anatase
TiO2 and the relaxed structure when one Ti atom has been
replaced by a Ge atom, we use the forces acting on the atoms
to move them to the equilibrium positions, where the forces
are smaller than the criterion and the corresponding total
energy has a minimum. The following steps are performed:
(i) Volume optimization: begin with the experimental
ratio of c/a, calculate the total energy as the function of
the unit cell volume, and obtain the lattice parameters
corresponding to the lowest energy.
(ii) Geometry minimization: upon the structure obtained
above, perform movements of the atomic positions
according to the calculated forces. The iteration was
stopped when the force on each atom was smaller than
1 mRy/a.u., and repeat step (i).
(iii) c/a Optimization: on the basis of (i) and (ii), calculate the
total energy with the various ratios of c/a, and find the
relaxed structure corresponding to the lowest energy.
In Table 1, we present the relaxed structure of the doped
anatase and the optimized structure of the pure one. For
comparison, we also list other experimental and theoretical
results. In general, the agreement of the calculated
structures with experiment is good. In particular, our

Table 1
The relaxed structure of the doped anatase TiO2 and the optimized structural parameters for pure anatase in this work, compared to experiments and other
theoretical results (only for pure)

a (Å) c (Å) dap (Å) deq (Å) (c/a)

Doped 3.814 9.591 1.990(Ti–O) 1.950(Ti–O) 2.515
1.906(Ge–O) 1.948(Ge–O)
Pure 3.823 9.612 1.997 1.954 2.514
FPLAPW [12] 3.692 9.471 1.948 1.893 2.566
PHF [22] 3.763 9.851 1.995 1.939 2.618
B3LYP [23] 3.7923 9.8240 1.9972 1.9509 2.590
TM [24] 3.744 9.497 1.967 1.916 2.536
Exp. 1a [21] 3.78479 [3] 9.51237 [12] 1.9799 [5] 1.9338 [1] 2.51332
Exp. 1b [21] 3.78216 [3] 9.50226 [12] 1.9788 [4] 1.9322 [1] 2.51239
Exp. 2 [25] 3.7842 [13] 9.5146 [15] 1.9797 [23] 1.9338 [5] 2.5143

The Exp. 1a [21] is obtained at 295 K, while the Exp. 1b [21] is at 15 K (exp., experiment). The italic values are derived from the experimental data.
 Q. Chen, H.-H. Cao / Journal of Molecular Structure: THEOCHEM 723 (2005) 135–138 137

Fig. 2. The band structure of the pure and doped anatase TiO2 as described in text. The top of the valence band is taken as the zero of energy.

calculated pure structure is in better agreement with
experiment for deq and c/a than other theoretical outcomes.
There are following two aspects in the comparison of the
pure and doped structures that attract our attention:
First, the size of the doped unit cell (a, c), is smaller than
that of the pure one, which can be seen in Table 1.
Second, the apical and equatorial Ti–O bond length of
the pure structure is 1.997 and 1.954 Å, while for the doped
structure the correspondences of Ge–O decrease to 1.906
and 1.948 Å, respectively.
With the pure and doped structure, we investigated the
band structure of the anatase TiO2 using GGA [16],

Fig. 3. Total and projected DOS for the doped anatase TiO2. The origin of the energy scale is taken at the Fermi level, as the vertical dotted line indicates.
Mainly of Ti states, which show two distinct structures, below and above 4.52 eV. The upper CB is mainly introduced by Ge states. The O states contribute the
valence bands (VB).
138 Q. Chen, H.-H. Cao / Journal of Molecular Structure: THEOCHEM 723 (2005) 135–138
respectively. The calculated band structure along the high-
symmetry directions of the BZ is presented in Fig. 2. The
origin of the energy scale is taken at the Fermi level. The
band structure is similar to that of the rutile and is very flat
as expected for a mostly ionic compound. The present
calculations of the pure anatase TiO2 is found to be similar
to that of the B3LYP calculations [23], while that of the
TM calculations [24] is not consistent with ours in the range
of Z to G.
With the pure structure, our calculation yields in the pure
anatase an indirect transition of 2.12 eV from the top of the
VB near X to the conduction band (CB) at G, while for the
doped unit cell, the corresponding band gap decrease to
1.96 eV.
Although both of them are smaller than that experimen-
tally observed due to the well-known shortcoming of the
GGA [26], but the narrowing trend of the energy gap should
be paid attention to in both the experimental and theoretical
studies.
To identify the contributions from various orbitals after
doping we also calculate the total and partial densities of
states (DOS), as shown in Fig. 3.
There are seven inequivalent atoms in the unit cell,
two Ti, one Ge and four O atoms. It can be seen that the
conduction bands (CB) below 7.41 eV consist mainly of
Ti states, which show two distinct structures, below and
above 4.52 eV. The upper CB is mainly introduced by
Ge states. The O states contribute the valence bands
(VB).
4. Conclusion
We have presented an ab initio study of the electronic
structure of the Ge doped anatase TiO2 using the highly
precise FP-LAPW with the exchange-correlation functional
of GGA.
The work can be summarized as follows:
(i) The fully optimized and relaxed structures were
obtained by using the forces acting on the atoms to
move them to the equilibrium positions, where the
forces are smaller than the criterion and the correspond-
ing total energy has a minimum.
(ii) The band structures of both pure and doped anatase
TiO2 were calculated. The density of states and the
electron density of the relaxed structure were also
obtained, which will be helpful to analyzing and
interpretation.
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