View Article Online

View Journal

RSC Advances
This article can be cited before page numbers have been issued, to do this please use: E. Zahedi, M.
Hojamberdiev and M. Bekheet, RSC Adv., 2015, DOI: 10.1039/C5RA13763B.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/advances
 Page 1 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

Electronic, Optical and Photocatalytic Properties of

Three-Layer Perovskite Dion-Jacobson Phase CsBa2M3O10

Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

(M=Ta, Nb): A DFT Study

RSC Advances Accepted Manuscript

Ehsan Zahedia,*, Mirabbos Hojamberdievb, Maged F. Bekheetc

a
Department of Physical Chemistry, Shahrood Branch, Islamic Azad University, Shahrood, Iran

b
Department of Environmental Science and Technology, Faculty of Engineering, Shinshu

University, 4-17-1 Wakasato, Nagano 380-8553, Japan

c
Fachgebiet Keramische Werkstoffe, Institut für Werkstoffwissenschaften und –technologien,

Fakultät III Prozesswissenschaften, Technische Universität Berlin, Hardenbergstraße 40, 10623

Berlin, Germany

*Corresponding author. Tel: +98 9122733755; Fax: +98 23 32344634

E-mail addresses: [email protected]; [email protected]

1
 RSC Advances Page 2 of 26
View Article Online
DOI: 10.1039/C5RA13763B

ABSTRACT

The structure, electronic and optical properties have been studied to consider photocatalytic

activity of three-layer perovskite Dion-Jacobson phase CsBa2M3O10 (M = Ta, Nb) using the
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

density functional theory (DFT) method with the plane-wave pseudo-potential in the frame of the

GGA proposed by Perdew, Burke, and Ernzerhof (PBE). CsBa2Ta3O10 and CsBa2Nb3O10 are

RSC Advances Accepted Manuscript

indirect band gap semiconductors with different type of M–O bonds from pure covalent to pure

ionic. According to the symmetry breaking of MO6 octahedra from Oh point group to

centrosymmetric (D4h) and non-centrosymmetric (C4v) point groups, the generation of local

internal fields, the promotion of electron-hole pairs separation in the very initial process of

photo-oxidation and the improvement in photocatalytic activity are suggested. Site and angular

projected density of states for CsBa2M3O10 show that the valence and conduction bands are made

mainly of O and M orbitals, therefore the presence of dipole moment at the MO6 octahedra will

play an important role in separating of electrons and holes. According to the optical properties

simulation the origin of interband transitions for CsBa2Ta3O10 and CsBa2Nb3O10 are from O-p and

M-d orbitals. CsBa2Ta3O10 and CsBa2Nb3O10 are UV-light-responsive photocatalysts with

plasmon energies 13.16 and 12.07 eV, respectively, which can possibly oxidize/decompose

organic pollutants and generate hydrogen from water splitting.

KEYWORDS:

Dion-Jacobson phase; DFT; Electronic structure; Optical properties; Photocatalytic activity

2
 Page 3 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

1. Introduction

Perovskites are inorganic compounds with a general chemical formula ABX3, where A and B are

two cations of different sizes and X is an anion, usually oxygen, that bonds to both cations. Most
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

perovskites have a cubic symmetry structure in which the B cation is in 6-fold coordination

surrounded by an octahedron of anions and A cation is in 12-fold cuboctahedral coordination. The

RSC Advances Accepted Manuscript

stability of cubic structure depends on the relative ionic size, in which a slight buckling and

distortion, such as tilting of BO6 octahedra, can reduces the coordination number of A and B cations

or both. The orthorhombic and tetragonal structures of perovskites are the result of changes in the

coordination numbers of cations. Perovskites can also have layered structures constructed of

negatively charged thin layers and cations in the interlayer space compensating negative charges

on the layers According to their chemical nature, three types of layered perovskites are known with

the general formulas of [Bi 2 O 2 ]A n −1B 2O 7 for Aurivillius (AV) phase,

A′[A n −1Bn O3n +1 ] Dion-Jacobson (DJ) phase, and A′2 [A n −1B n O3n +1 ] Ruddlesden-Popper (RP)

phase; where Aʹ is monovalent alkali metal ion, A is divalent alkaline earth metal ion, and B is

tetravalent or pentavalent transition metal ion. In the AV phase, the intruding layer is

[Bi 2O 2 ]2 + ion, whereas the intruding layer is an alkali metal in the DJ and RP phases. In the DJ and

RP phases, the thickness of perovskite slabs relies on the number of BO6 octahedral (n) corner
1-4
shared along the c-axis . The DJ and RP layered perovskites have various interesting physical

and chemical properties, such as ionic conductivity due to ion exchange of alkali ions with molten

salts or under acidic conditions, dielectricity, superconductivity, luminescence, photocatalytic

1, 5
activity, magnetism, and giant magnetoresistivity . In this work, structure, electronic, optical,

and photocatalytic properties of two members of three-layer perovskite DJ family, cesium

dibarium tritantalate (CsBa2Ta3O10) and cesium dibarium triniobate (CsBa2Nb3O10) were

3
 RSC Advances Page 4 of 26
View Article Online
DOI: 10.1039/C5RA13763B

systematically studied by applying density functional theory (DFT) calculations. Hereafter,

CsBa2Ta3O10 and CsBa2Nb3O10 are denoted as CBTO and CBNO, respectively.

2. Computational methodology
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

The experimental crystal structural data of CsBa2M3O10 (M = Ta, Nb) were taken as initial

geometries 1, 6. The Cambridge Serial Total Energy Package (CASTEP) code 7, which uses a plane

RSC Advances Accepted Manuscript

wave expansion technology in reciprocal space, was used. The generalized gradient approximation

(GGA) of Perdew, Burke, and Ernzerhof (PBE) was used for the electronic exchange-and

correlation interactions 8. The core-valence interactions were described by the Vanderbilt ultrasoft

pseudo-potential 9 with the valence configurations 5s2 5p6 6s1 for Cs, 5s2 5p6 6s2 for Ba, 4s2 4p6 4d4

5s1 for Nb, 5s2 5p6 5d3 6s2 for Ta and 2s2 2p4 for O, in order to allow calculations to be performed

with the lowest possible cut-off energy with minimum contribution from the core region. The

crystal reciprocal-lattice and integration over the Brillouin zone were performed using the

Monkhorst-Pack 10 grid of 12 × 12 × 3 for CBTO and 13 × 13 × 3 for CBNO, in which the spacing

of grid points was smaller than 0.03 Å-1 for all calculations. The
11
Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm has been used for geometry

optimizations, and the convergence parameters were as follows: the plane wave basis set energy

cut-off 550 eV, total energy convergence tolerance 1 × 10-5 eV/atom, self-consistent field tolerance

2 × 10-6 eV/atom, maximum force 0.03 eV/Å, maximum stress 0.05 GPa, and maximum

displacement 0.001 Å. The separation between k-points in the band structure calculations was

adopted by 0.005 Å-1.

3. Results and discussion

The conventional cell of the DJ phase CsBa2M3O10 (M = Ta, Nb) is displayed in Figure 1a.

4
 Page 5 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

(a)
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

RSC Advances Accepted Manuscript

(b)

D4h C4v
Figure 1. (a) Crystal structure and corresponding polyhedron structure of Dion-Jacobson phase

CsBa2M3O10 (M = Ta, Nb). The cesium, barium, tantalum/niobium, and oxygen atoms are

represented by purple, green, blue, and red spheres, respectively. In the polyhedron structure, MO6

octahedral environments are shown by blue color. (b) Distortion of MO6 octahedral (Oh) to

centrosymmetric (D4h) and non-centrosymmetric (C4v). The tantalum/niobium and oxygen atoms

are represented by blue and red spheres, respectively.

5
 RSC Advances Page 6 of 26
View Article Online
DOI: 10.1039/C5RA13763B

The crystalline structures of tetragonal CBTO and CBNO with space group of P4/mmm (No. 123)

contain one cesium atom, two barium atoms, three tantalum/niobium atoms, and ten oxygen

atoms in a unit cell. In these crystal structures, Cs and Ba atoms are in environment of MO6
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

octahedral units, in which there are one type of Cs atom (1 atom with site of 1d), one type of Ba

atom (2 atoms with site of 2h), two types of M atoms (1 atom with site of 1a and 2 atoms with

RSC Advances Accepted Manuscript

site of 2g), and four types of O atoms (2 atoms with site of 2f, 4 atoms with site of 2g, and 4

atoms with site of 4i). The optimized crystallographic parameters and final atomic positions of

tetragonal CBTO and CBNO are listed in Table 1 and compared with the experimental values.

Table 1. Optimized crystallographic parameters and final atomic positions of tetragonal CBTO
and CBNO compared with the experimental values from Ref. [1,6]*
Wyckoff
Crystallographic parameters Atom x y z
position
CsBa2Ta3O10 (CBTO) Cs 1d 0.5 (0.5) 0.5 (0.5) 0.5 (0.5)
a = 4.1362 (3.9647) Å Ba 2h 0.5 (0.5) 0.5 (0.5) 0.1439 (0.1442)
b = 4.1362 (3.9647) Å Ta (1) 1a 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
c = 16.2527 (15.7392) Å Ta (2) 2g 0.0 (0.0) 0.0 (0.0) 0.2847 (0.2985)
α=β=γ=90˚ O (1) 2f 0.0 (0.0) 0.5 (0.5) 0.0 (0.0)
O (2) 2g 0.0 (0.0) 0.0 (0.0) 0.1272 (0.1280)
O (3) 4i 0.0 (0.0) 0.5 (0.5) 0.2587 (0.2680)
O (4) 2g 0.0 (0.0) 0.0 (0.0) 0.4009 (0.4030)

CsBa2Nb3O10 (CBNO) Cs 1d 0.5 (0.5) 0.5 (0.5) 0.5 (0.5)

a = 3.9915 (3.9766) Å Ba 2h 0.5 (0.5) 0.5 (0.5) 0.1435 (0.1437)
b = 3.9915 (3.9766) Å Nb (1) 1a 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
c = 16.1099 (15.5792) Å Nb (2) 2g 0.0 (0.0) 0.0 (0.0) 0.2900 (0.2908)
α=β=γ=90˚ O (1) 2f 0.0 (0.0) 0.5 (0.5) 0.0 (0.0)
O (2) 2g 0.0 (0.0) 0.0 (0.0) 0.1226 (0.1220)
O (3) 4i 0.0 (0.0) 0.5 (0.5) 0.2654 (0.2680)
O (4) 2g 0.0 (0.0) 0.0 (0.0) 0.3993 (0.4020)
*
Experimental values are given in parenthesis.

6
 Page 7 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

As shown, the calculated crystallographic values and atomic positions are close to the

experimental values. The main difference between the theoretical and experimental values is due

to two factors: i) the experimental measurements were performed at 298 K, while the theoretical
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

calculations were done in the ground state condition under absolute zero temperature and ii) the
12
known DFT limitation is due to certain simplifications and approximations . The crystal

RSC Advances Accepted Manuscript

structures of CBTO and CBNO are built up of columns of apex-sharing octahedral running

parallel to the c-axis, which are linked by apex oxygen. The calculated and experimental results in

Table 2 showed that the MO6 octahedra in CBTO and CBNO is distorted from Oh point group to

centrosymmetric (D4h) and non-centrosymmetric (C4v) point groups, as shown in Figure 1b. The

interlayer cesium ion is located in the channel between four C4v polyhedra, whereas barium ions

are located in the channel between two D4h and two C4v polyhedra. In the MO6 group with D4h

point group the axial M–O bond lengths are slightly different than that of equatorial M–O bonds,

and the O–M–O bond angles are exactly 90°. The calculated M–O bond lengths in Table 2 show

that the axial and equatorial M–O bond lengths in CBTO are 2.068 and 2.067 Å, respectively,

whereas for CBNO are 1.975 and 1.996 Å. Therefore, the center of gravity is located at the M

position, and consequently, dipole moment in the local MO6 groups with D4h point group is zero.

On the other hand, in the MO6 group with C4v point group, two axial M–O bond lengths are

significantly different, that is, 2.559 and 1.889 Å for CBTO and 2.696 and 1.761 Å for CBNO.

Also, the equatorial M–O bond lengths are 2.111 and 2.034 Å for CBTO and CBNO, respectively.

The various M–O bonds and the deviated M–O–M angles from 90° lead to the centers of the

positive and negative charges not locating at the same point. The separation between the centers of

the positive and negative charges generates dipole moment in the local MO6 groups with C4v point

group. The local internal fields due to the dipole moments are suggested to promote the separation

7
 RSC Advances Page 8 of 26
View Article Online
DOI: 10.1039/C5RA13763B

of electron-hole pairs in the very initial process of photo-oxidation and to improve photocatalytic

activity 13.

Table 2. The calculated Mulliken bond population, population ionicity, and bond lengths of
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

tetragonal BCTO and BCNO compared with the experimental values from Ref. [1,6]

RSC Advances Accepted Manuscript

Bond length (Å)
Sample Bond (type) Population Ionicity
Exp. Cal.
Ta1–O1 (ax) 0.97 0.03 2.014 2.068
Ta1–O2 (eq) 0.39 0.79 1.982 2.067
CsBa2Ta3O10 (CBTO) Ta2–O1 (ax) 0.08 ~1 2.542 2.559
Ta2–O3 (eq) 0.88 0.13 2.011 2.111
Ta2–O4 (ax) 1.03 0.03 1.786 1.889
O 4… O 5 3.053 3.221

Nb1–O1 (ax) 0.07 ~1 1.901 1.975

Nb1–O2 (eq) 0.66 0.40 1.988 1.996
CsBa2Nb3O10 (CBNO) Nb2–O1 (ax) -0.01 ~1 2.629 2.696
Nb2–O3 (eq) 0.83 0.19 2.019 2.034
Nb2–O4 (ax) 0.90 0.11 1.732 1.761
O 4… O 5 3.054 3.246

To understand the bonding nature of each M–O bond, the Mulliken bond populations were

calculated. The Mulliken bond population is a measure of spatial charge density between bonding

atoms, and this quantity does not totally depend on the valence charge transfer along the bond

axis 14. A high total overlap (bond) population indicates a high degree of covalency in the bond,

and the positive and negative values indicate bonding and antibonding states, respectively 15. On

the other hand, the percentage of covalence nature of a bond can be calculated using population

ionicity (Pi) from the following equation 14:

P −P
− c
P
Pi = 1 − e (1)

where P is the total overlap population of the bond and Pc is the bond population for a pure

covalent bond. The lower limit, i.e., Pi = 0 indicates a pure covalent bond, whereas the upper limit

8
 Page 9 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

i.e., Pi = 1 indicates a pure ionic bond. Here, the value of Pc is assumed to be equal to 1. The

calculated total overlap population and population ionicity of each M–O bond in tetragonal

CBTO and CBNO are also given in Table 2. It is found that Ta2–O1 (ax), Nb1–O1 (ax), and Nb2–O1
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

(ax) are pure ionic bonds, whereas Ta1–O1 (ax) and Ta2–O4 (ax) are pure covalent bonds.

Moreover, Ta1–O2 (eq) and Nb2–O4 (ax) bonds have ionic-covalence and highly covalent nature,

RSC Advances Accepted Manuscript

respectively.

It is known that the Kohn-Sham band structure underestimates systemically the band gap of
16
insulators and semiconductors by about 30-100% due to the known shortcoming of
17
exchange-correction function in describing excited states . To illustrate the problem, the

underestimated band gap can be corrected by scissors operator according to the experimental

values. This operator rigidly shifts the unoccupied conduction band states with respect to the

completely occupied valence band states to bring the minimum band gap in line with

experimental values. Diffuse reflectance UV-vis spectroscopy is a simple method for measuring

the experimental band gap. The observed experimental UV-Vis absorption spectra for CBTO and

CBNO samples are shown in Figure 2a, and the experimental band gaps can be calculated using

cut-off wavelength by the following equation:

1239.84
Eg = (2)
λ cut off

The measured UV-Vis absorption cut-off wavelengths for CBTO and CBNO samples are about

350 nm (3.54 eV) and 450 nm (2.74 eV), respectively.

The calculated band structures of CBTO and CBNO along the high symmetry directions in the

first Brillouin zone are shown in Figure 2b.

9
 RSC Advances Page 10 of 26
View Article Online
DOI: 10.1039/C5RA13763B

(a)
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

RSC Advances Accepted Manuscript

(b)
CBTO CBNO

Z A M G Z Z A M G Z

(c)

Figure 2. (a) Experimental UV-Vis absorption spectra of CBTO (blue) and CBNO (red). The

cut-off wavelength positions are shown by arrows. (b) The calculated band structures of CBTO and

CBNO. The Fermi energy (EF) is set to be 0 eV and is marked by a horizontal dashed line. (c) The

first Brillouin zone of CBTO and CBNO in the reciprocal lattice. The red line corresponds to the

path of the band structure diagram, and g1, g2, and g3 denote the reciprocal vectors.
10
 Page 11 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

The Fermi energy level, EF, is chosen to be located at the position of 0 eV. The coordinates of the

special points of the Brillouin zone (Figure 2c) in terms of unit vectors of the reciprocal lattice

are G (0, 0, 0), Z (0, 0, 0.5), R (0, 0.5, 0.5), X (0, 0.5, 0), A (0.5, 0.5, 0.5), and M (0.5, 0.5, 0). For
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

CBTO and CBNO, the uncorrected band gap energies are 1.42 and 1.49 eV, respectively, which

are smaller than the experimentally obtained band gap energies. Therefore, the underestimated

RSC Advances Accepted Manuscript

band gaps were corrected by applying scissors operators 2.12 and 1.25 eV for CBTO and CBNO,

respectively. As shown in Figure 2b, for CBTO and CBNO, the valence band maximum (VBM)

and conduction band minimum (CBM) are located at different points of the Brillouin zone,

indicating that these compounds are indirect band gap semiconductors. The second derivative of

band dispersion band-edge energy as a function of the wave vector k is related to the inverse of

effective mass of electron or hole at the band extremes. For tetragonal crystals, the effective masses
18
of either the hole or electron in the [100], [010] directions are equal . As can be seen from the

graphical view of band structures, the valence and conduction bands in the [0 0 1] direction are

almost flat and less dispersive compared to the [0 1 0] and [1 0 0]. The higher dispersive

characteristics of the conduction and valence bands along the [0 1 0] and [1 0 0] directions

indicate the low effective masses of electrons and holes in the CBTO and CBNO with respect to

the [0 0 1] direction. On the other hand, the recombination of photo-generated charge carriers

along the [0 0 1] direction in the CBTO and CBNO semiconductors with indirect band gaps are

inefficient.

In order to analyze the composition of the electronic band structures, the corresponding total,

site- and l-projected density of states (DOS) diagrams and their projected electronic wave

functions (PEWF) are shown in Figures 3-6. It is exigent to mention that the plane wave basis set

and ultrasoft pseudo-potential present only the wave functions of the valence electron of atoms.

11
 RSC Advances Page 12 of 26
View Article Online
DOI: 10.1039/C5RA13763B

The total DOS diagrams and their PEWFs in the (1 0 0) plane for CBTO and CBNO are presented

in Figures 3a and b to illustrate the interactions of O–M and O–Ba.

(a) E3
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

E2 E5
E6

RSC Advances Accepted Manuscript

E4
E1

(b)
CBTO

CBNO

Figure 3. (a) Total density of states for CBTO (red) and CBNO (blue). The Fermi energy (EF) is

set to be 0 eV. (b) Total charge density distribution for CBTO and CBNO in the (1 0 0) plane in

order to illustrate the M–O and Ba–O bonds.

12
 Page 13 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

It can be seen that the charge density contours for O and Ba atoms in the (1 0 0) plane containing

O, Ba, and Cs atoms are spherical, suggesting a highly ionic bonding nature for O–Ba. On the

other hand, the charge density contours in the (1 0 0) plane containing O and M atoms
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

corroborate that there are highly ionic and highly covalent characters between O and M atoms in

different O–M interactions. The analysis of PEWF indicates that the bonding nature in CBTO and

RSC Advances Accepted Manuscript

CBNO is ionic and covalent. The total DOS can be projected into its partial components with
19
respect to different atoms by solving the eigenvalues and eigenvectors in the Brillouin zone .

The site- and l-projected DOS diagrams together with their PEWFs for conduction band

minimum and five parts of valence band are shown in Figures 4-6. For both systems, the quality

of PDOS results is similar. The lowest-lying state from -20 to -18 eV (E1 region) is mainly due to

Cs-5s and Cs-6s states. The second region in a higher energy range (E2 region) from -18 to -15 eV

is essentially contributed by O-2s states with a minor admixture of Ba-5p and Ta-5s/6s/5p/5d

states for CBTO or Nb-4s/5s/4p/4d states for CBNO. The PEWF of this region shows a weak

hybridization between O atom and Ba, Ta or Nb atoms forming an ionic bonding. The next region

(E3 region) from -11 to -9 eV mainly comes from Ba-5p states with a small contribution of O-2s

states. The PDOS and PEWF of this region show weak s-p hybridization between O and Ba atoms

forming an ionic bonding. The E4 region is predominantly composed of Cs-5p which is slightly

hybridized with O-2p. The role of Ta or Nb electronic states in this energy region is very minor.

At the top of valence band (E5 region), O-2p is overlapped with Ta-5d or Nb-4d, indicating p-d

hybridization between O and Ta or Nb atoms forming a covalent bonding. The conduction band

region (E6 region) is mainly from O-2p and Ta-5d or Nb-4d states. Since the valence and

conduction bands (E5 and E6 regions) are mainly composed of O and Ta or Nb orbitals, the band

gap excitation can occur at the MO6 units; consequently, the presence of a dipole at the MO6

units will play a significant role in separating of electrons and holes.

13
 RSC Advances Page 14 of 26
View Article Online
DOI: 10.1039/C5RA13763B

(a) (b)
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

RSC Advances Accepted Manuscript

Figure 4. Site and angular projected density of states for CBTO (a) and CBNO (b). Red, green, and

blue lines represent s, p, and d orbitals, respectively. The Fermi energy (EF) is set to be 0 eV.

14
 Page 15 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

E6
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

E5

RSC Advances Accepted Manuscript

E4

E3

E2

E1

Figure 5. Projected wave function contour plots for CBTO at six different energy ranges in the (1

0 0) plane illustrating the M–O and Ba–O bonds.

15
 RSC Advances Page 16 of 26
View Article Online
DOI: 10.1039/C5RA13763B

E6
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

E5

RSC Advances Accepted Manuscript

E4

E3

E2

E1

Figure 6. Projected wave function contour plots for CBNO at six different energy ranges in the (1

0 0) plane illustrating the M–O and Ba–O bonds.

16
 Page 17 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

The optical property of a system is related to the transverse dielectric function ε(q,ω), where q is

the momentum transfer in the photon-electron interaction and ω is the angular frequency for

excitation. When the momentum transfer from the initial state to the final state is neglected, the
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

complex dielectric function can be defined by the following mathematical relation 20:

ε (ω) = ε1 (ω) + iε2 (ω) (3)

RSC Advances Accepted Manuscript

The imaginary part of the complex dielectric function is related to the interband and intraband

optical transitions between the different special k points at the first irreducible Brillouin zone.

The intraband transitions are only important for metals; therefore, only direct and indirect

interband transitions can be considered for semiconductors21, 22. ε2(ω) can be calculated from

direct numerical evaluations of the momentum matrix elements of the electric dipole operator

between the conduction and valence band wave functions 23, 24:

2e 2 π 2
ε 2 (ω ) = ∑
ωε 0 k , v,c
ψ ck u.r ψ kv δ(E ck − E kv − E) (4)

where u is the polarization vector of the incident electric field, r is the electron’s radius vector,

and e is electric charge, ψ ck and ψ kv are the conduction and valence band wave functions at k,

respectively, and ε0 is the vacuum permittivity. The summation of the equation is applied over all

states from the occupied and empty bands, with their wave functions obtained in a numerical

form after the optimization of the crystal structure. The real part, ε1(ω), of the dielectric function

can be obtained from the imaginary part by using the Kramers-Krönig dispersion equation 24, 25:

2 ∞ Ω ε 2 (Ω )
π ∫0 Ω 2 − ω 2
ε1 (ω) = 1 + P dΩ (5)

where P is the Cauchy principal value of the integral.

All optical properties were calculated with calculation geometry polycrystalline, instrumental

smearing 0.5 eV. The vertical rigid shift of conduction band states (scissors operators) 2.12 and

17
 RSC Advances Page 18 of 26
View Article Online
DOI: 10.1039/C5RA13763B

1.25 eV was applied for CBTO and CBNO, respectively, due to underestimation of excitation

energies with the DFT calculations. Figure 7a shows the calculated average imaginary and real

parts of dielectric constant of CBTO and CBNO. The real part of dielectric function at zero
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

frequency shows that the static dielectric constants for CBTO and CBNO are 2.856 and 2.904,

respectively. The square root of static dielectric constant gives an estimation of the refractive

RSC Advances Accepted Manuscript

index of CBTO and CBNO, which are 1.69 and 1.70, respectively. The negative values of the real

part of dielectric function are due to damping of electromagnetic wave, and zero values indicate

that longitudinally polarized waves are possible 20. The imaginary part of dielectric function starts

at 3.86 and 3.18 eV for CBTO and CBNO, respectively. Since the direct interband transitions

have a significant contribution to the ε2(ω) with respect to indirect interband transitions, the

maximum of the main peak for CBTO and CBNO belongs to A → A and M → M direct

transitions. The main portion of the mentioned peaks for CBTO and CBNO is due to O-2p → Ta-5d

and O-2p → Nb-4d interband transitions, respectively, whereas Ta-5d → O-2p and Nb-4d → O-2p

interband transitions have smaller portion. In the electromagnetic radiation, electric and magnetic

fields oscillate perpendicular to each other and perpendicular to the wave propagation. Interband

and intraband transitions are resulted from the effect of electric field of photon on the complex

dielectric function 26.

18
 Page 19 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

(a)
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

RSC Advances Accepted Manuscript

(b)

(c)

Figure 7. (a) Real (solid line) and imaginary (dashed line) parts of the dielectric function of

CBTO (red line) and CBNO (blue line). (b) Energy loss functions of CBTO (red line) and CBNO

(blue line) as a function of photon energy. (c) Absorption spectra of CBTO (red line) and CBNO

(blue line) as a function of photon energy.

19
 RSC Advances Page 20 of 26
View Article Online
DOI: 10.1039/C5RA13763B

When electrons pass through a homogeneous material, some electrons undergo inelastic scattering

which means that they loss energies, also their paths slightly and randomly deflect. The energy loss

function (ELF) is related to the dielectric function, as follow 27:

Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

 −1  ε 2 ( ω)
L(ω) = Im  = (6)
 ε (ω)  ε1 (ω) + ε2 (ω)
2 2

RSC Advances Accepted Manuscript

Figure 7b shows the energy loss function of CBTO and CBNO. The prominent peaks of ELF are

located at 13.16 and 12.07 eV for CBTO and CBNO, respectively, where electrons are originally

unbound to their lattice sites and start plasma oscillation. The collective oscillations of free electron

gas density is plasmon, and the corresponding energy is so-called plasmon energy (Ep). The values

of plasmon energies are located in the ultra violet (UV) region.

The quantity and nature of the optical band gap can be calculated using the conventional Tauc

method from the optical absorption spectra. The absorption coefficient α(E) indicates the fraction

of absorbed light when it passes through the material, and is written as 24:

2ω ε1 (ω) 2 + ε2 (ω)2 - ε1 (ω)

α (ω ) = (7)
c

where c is the velocity of light. Two types of optical transitions, direct and indirect, can be

investigated by following relation expression that is proposed by Tauc 28:

α ( E ) E = A( E − Egdirect ) 0.5 + B ( E − Egindirect ± E phonon ) 2 (8)

where A and B are fitting parameters, Egdirect and Egindirect are direct and indirect optical gaps, Ephonon

is the phonon energy and E is incident photon energy. The straight line segment in (αE)2 indicates a

direct optical band gap, whereas the straight line segment in (αE)0.5 indicates an indirect optical

band gap.

20
 Page 21 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

The calculated optical absorption curves in Figure 7c show that the CBTO and CBNO are poor

absorber of visible light, or in other words, are ultra violet (UV) light-responsive photocatalysts.
29
Based on ISO standard ISO-21348 , main absorption of incident photon for CBTO and CBNO
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

occurs at the vacuum ultra violet region. Extrapolation of the linear portion of Tauc plots (Figure

8) with the abscissa clearly indicates that CBTO and CBNO are indirect semiconductors so that

RSC Advances Accepted Manuscript

optical and electronic gaps coincide. The indirect optical gap values indicate that CBTO and

CBNO can absorb near UV light and violet light in the visible region, respectively.

(a)

(b)

Figure 8. Tauc plots of (a) CBTO and (b) CBNO. (αE)0.5 for indirect gap (blue line) and (αE)2 for

direct gap (red line).

21
 RSC Advances Page 22 of 26
View Article Online
DOI: 10.1039/C5RA13763B

The positions of valence and conduction bands of a semiconductor and the redox potentials of an

adsorbate are important factors for the oxidation and reduction capabilities of the semiconductor

to undergo photoinduced electron transfer to the adsorbed species on its surface. The suitable
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

potential level of the acceptor species is thermodynamically required to be more positive than the

conduction band potential of the semiconductor (ECB), while the potential level of the donor

RSC Advances Accepted Manuscript

needs to be more negative than the valence band position of the semiconductor (EVB) in order to
30
donate an electron to the vacant hole . The band edge positions of CBTO and CBNO were

calculated using empirical formulas, as follows 24, 29, 31-35:

E VB = χ − Ee + 0.5 EgOptical (9)

ECB = EVB − EgOptical (10)

where Ee is the energy of free electrons on the hydrogen scale (approximately 4.50 eV) and χ is

electronegativity of a semiconductor, which is the geometric mean of the electronegativities of

the isolated component atoms and is expressed, as follows 36:

1
 P  P
χ ≈  Π χ k  (11)
 k =1 

where P is the number of atoms in the semiconductor and k = 1, 2, 3, …, P. The values of

electronegativity of CBTO and CBNO are 5.40 and 5.37 eV, respectively, which were calculated

from the experimental values of electronegativity (i.e., Ba = 2.40 eV, Cs = 2.18 eV, Ta = 4.11
37
eV, Nb = 4.00, and O = 7.54 eV) . The relative dispositions of VB and CB edge potentials of

CBTO and CBNO with respect to vacuum scale and NHE (normal hydrogen electrode) are

displayed in Figure 9.

22
 Page 23 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

2H2O + 2e → H2 + 2OH• E° = -0.83 V

O2 + 2e → O2•- E° = -0.33 V
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

2H+ + 2e → H2 E° = 0.00 V

RSC Advances Accepted Manuscript

4H+ + O2 + 4e → 2H2O E° = 1.23 V

H2O2 + 2H+ + 2e → 2H2O E° = 1.77 V

O3 + 2H+ + 2e → O2 + H2O E° = 2.07 V

Figure 9. Relative dispositions of VB and CB potentials of CBTO and CBNO with respect to

vacuum scale and NHE.

From the viewpoint of positions of VB and CB edge potentials, CBTO and CBNO are suitable

photocatalysts without the need for co-catalysts. The VB potentials of CBTO and CBNO are more

positive than the oxidation potential of O2/H2O (1.23 V), H2O2/H2O (1.77 V), and O3/H2O (2.07

V). Therefore, the photogenerated holes can oxidize H2O to produce active species O2, H2O2, and

O3. These active species can further oxidize/decompose organic pollutants and dye molecules. The

CB potential of CBTO is more negative than the redox potential of H2O/OH• (-0.83 V); therefore,

the photogenerated electrons can produce H2 and active species O2•- and OH•, while the

photogenerated electrons in CBNO can produce H2 and O2•-. In addition to O2•- and OH• are active

species to decompose organic pollutants, CBTO and CBNO are good candidate for photocatalytic

hydrogen generation from water splitting.

23
 RSC Advances Page 24 of 26
View Article Online
DOI: 10.1039/C5RA13763B

4. Conclusions

The electronic, optical, and photocatalytic properties of three-layer perovskite Dion-Jacobson

phase CsBa2M3O10 (M = Ta, Nb) have been studied with the plane wave pseudo-potential using the
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

density functional theory (DFT) method considering the exchange-correlation function within the

generalized gradient approximation (GGA) proposed by Perdew, Burke, and Ernzerhof (PBE), as

RSC Advances Accepted Manuscript

implemented in the CASTEP code. The structural study showed that the symmetry of the MO6

octahedra in CsBa2Ta3O10 and CsBa2Nb3O10 is reduced from Oh point group to centrosymmetric

(D4h) and non-centrosymmetric (C4v) point groups, leading to the special optical properties and

photocatalytic activities. The population ionicity index indicated that there are different

percentages of covalence nature in the M–O bonds from pure covalent to pure ionic. The band

structures and Tauc plots showed that CsBa2Ta3O10 and CsBa2Nb3O10 are ultra violet (UV)

light-responsive photocatalysts with indirect band gap. The density of states spectrums and

projected electronic wave functions were studied in detail to illustrate the origin of photocatalytic

activity and nature of M–O and Ba–O bonds. CsBa2Ta3O10 and CsBa2Nb3O10 with plasmon

energies of 13.16 and 12.07 eV, respectively, were suggested to possibly oxidize/decompose

organic pollutants and generate hydrogen from water splitting under UV light.

Notes and References

1. V. Thangadurai, P. Schmid-Beurmann and W. Weppner, J. Solid. State. Chem., 2001, 158,

279-289.
2. J. Gopalakrishnan and V. Bhat, Inorg. Chem., 1987, 26, 4299-4301.
3. M. Richard, L. Brohan and M. Tournoux, J. Solid. State. Chem., 1994, 112, 345-354.
4. M. Dion, M. Ganne and M. Tournoux, Mat. Res. Bull., 1981, 16, 1429-1435.
5. S. H. Byeon and K. Park, J. Solid. State. Chem., 1996, 121, 430-436.
6. M. Hojamberdiev, M. F. Bekheet, E. Zahedi, H. Wagata, K. Yubuta, A. Gurlo, K. Domen
and K. Teshima, Mater. Chem. (submitted). .
7. S. J. Clark, M. D. Segall, C. J. Pickard, P. J. Hasnip, M. J. Probert, K. Refson and M. C.
Payne, Z. Kristallogr., 2005, 220, 567-570.
8. J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
24
 Page 25 of 26 RSC Advances
View Article Online
DOI: 10.1039/C5RA13763B

9. D. Vanderbilt, Phys. Rev. B, 1990, 41, 7892-7895.

10. J. D. Pack and H. J. Monkhorst, Phys. Rev. B, 1977, 16, 1748-1749.
11. B. G. Pfrommer, M. Cote, S. G. Louie and M. L. Cohen, J. Comput. Phys., 1997, 131,
133-140.
12. Z. Zhao, Z. Li and Z. Zou, Phys. Chem. Chem. Phys., 2011, 13, 4746-4753.
13. J. Sato, H. Kobayashi and Y. Inoue, J. Phys. Chem. B, 2003, 107, 7970-7975.
Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

14. J. He, E. Wu, H. Wang, R. Liu and Y. Tian, Phys. Rev. Lett., 2005, 94, 015504.
15. S. Goumri-Said, H. Ozisik, E. Deligoz and M. Benali-Kanoun, Semicond. Sci. Technol.,
2013, 28, 085005.

RSC Advances Accepted Manuscript

16. M. K. Y. Chan and G. Ceder, Phys. Rev. Lett., 2010, 105, 196403.
17. J. Yu, Q. Xiang and M. Zhou, Appl. Catal. B, 2009, 90, 595-602.
18. J. Feng and B. Xiao, J. Phys. Chem. Lett., 2014, 5.
19. S. Goumri-Said, H. Ozisik, E. Deligoz and M. B. Kanoun, Semicond. Sci. Technol., 2013,
28, 085005.
20. C. Y. Yang and R. Zhang, Chin. Phys. B, 2014, 23, 026301.
21. J. Feng, B. Xiao, J. C. Chen and C. T. Zhou, Solid State Sci., 2009, 11, 259-264.
22. T. Mahmood, C. Cao, F. K. Butt, H. Jin, Z. Usman, W. S. Khan, Z. Ali, M. Tahir, F. Idrees
and M. Ahmed, Physica B, 2012, 407, 4495-4501.
23. M. G. Brik, J. Phys. Condens. Matter., 2013, 25, 345802.
24. E. Zahedi, Superlattice Microst., 2015, 81, 49-63.
25. R. Paschotta, Encyclopedia of Laser Physics and Technology, Wiley-VCH, New York, 1st
edn., 2008.
26. S. K. Tripathy and V. Kumar, Mat. Sci. Eng. B, 2014, 182, 52-58.
27. T. Mahmood, C. Cao, W. S. Khan, Z. Usman, F. K. Butt and S. Hussain, Physica B, 2012,
407, 958-965.
28. M. Meinert and G. Reiss, J. Phys. Condens. Matter., 2014, 26, 115503.
29. J. Liu, S. Chen, Q. Liu, Y. Zhu and Y. Lu, Comp. Mater. Sci, 2014, 91, 159-164.
30. A. L. Linsebigler, G. Lu and J. T. Yates, Chem. Rev., 1995, 95, 735-758.
31. H. Chen, L. Ding, W. Sun, Q. Jiang, J. Hu and J. Li, RSC Adv., 2015, 5, 56401-56409.
32. S. Zhong, F. Zhang, W. Lu, T. Wang and L. Qu, RSC Adv., 2015, 5, 68646-68654.
33. G. Zhang, W. Zhang, J. C. Crittenden, Y. Chen, D. Minakata and P. Wang, Chin. J. Catal.,
2013, 34, 1926-1935.
34. Q. Zhang, H. Wang, S. Hu, G. Lu, J. Bai, X. Kang, D. Liuab and J. Gui, RSC Adv., 2015, 5,
42736-42743.
35. Z. Zhao, J. Tian, D. Wang, X. Kang, Y. Sang, H. Liu, J. Wang, S. Chen, R. I. Boughton and
H. Jiang, J. Mater. Chem., 2012, 22, 23395-23403.
36. A. Chakraborty, R. Das and P. K. Chattaraj, Computational and Experimental Chemistry:
Developments and Applications, Apple Academic Press, Inc, Canada, 2013.
37. R. G. Pearson, Inorg. Chem., 1988, 27, 734-740.

25
 RSC Advances Page 26 of 26
View Article Online
DOI: 10.1039/C5RA13763B

Table of Contents Entry

Published on 05 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 05/10/2015 10:53:05.

2H2O + 2e → H2 + 2OH• E° = -0.83 V

RSC Advances Accepted Manuscript

O2 + 2e → O2•- E° = -0.33 V
2H+ + 2e → H2 E° = 0.00 V

4H+ + O2 + 4e → 2H2O E° = 1.23 V

H2O2 + 2H+ + 2e → 2H2O E° = 1.77 V

O3 + 2H+ + 2e → O2 + H2O E° = 2.07 V

This work discloses structural, electronic and optical properties of three-layer perovskite Dion-
Jacobson phase CsBa2M3O10 (M = Ta, Nb) using the DFT method. These semiconductors are
UV-light-responsive photocatalysts.