Local Structure and Raman Spectrum of

Na0.5Bi0.5TiO3

M. K. Singh
Laser Materials Development and Devices Division
Raja Ramanna Centre for Advanced Technology
Indore 452 013 (INDIA)

Sodium Bismuth Titanate

(Na0.5Bi0.5TiO3)

Structure: Perovskite
Crystal Class: Rhombohedral
Space Group: R3c (at 300K)
Lattice Parameter: a=5.48, c=13.42 (R3cH)
Structural Transitions in NBT:

Pm3m

P4bm (P4/mbm)

R3c
(>540oC)

(540-500oC)

(500oC- 400oC)

(< 300oC)

Dielectric Anomalies in NBT:

o
o
o
T
=
300
C,
T
=
275
C,
T
=
180
C,
m
RT
d
G. O. Jones and P. A. Thomas, Acta Cryst. (2002). B58, 168-178
Y. Hiruma, H. Nagata, and T. Takenaka, J. Appl. Phys. 104 (2008) 124106

(400-300oC)

Literature
Group

Method

System

Space
group

J. A. Zvirgzds (1982)

X-ray diffraction

Rhom.

R3m

S. B. Vakhrushev (1983)

Neutron diffraction

Rhom.

R3c

Soukhojak et al. (2000)

Electron diffraction

Tetra.

-----

Jones et al (2000)

Neutron diffraction

Tetra.

P4bm

Jones et al (2002)

Neutron diffraction

Rhom.

R3c

A. Pietraszko et al (2006)

X-ray diffraction

Rhom.

R3c

Balagurov, A. M. (2006)

Neutron diffraction

Rhom.+Tetra.

----------

E. Aksel et al (2011)

X-ray diffraction

Monoclinic

Cc

Group

Space
group

Rp

Rwp

Jones et al
(2000)

P4bm

5.01

6.47

Jones et al
(2002)

R3c

5.90

7.80

E. Aksel
(2011)
Our result

Cc

R3c

5.87

9.30

8.09

11.40

In ten sity (a rb . u n its)

Observed
Calculated
Difference

x=0.00

In te n s ity ( a r b . u n its )

Ambiguity in structure, calculated

from X-ray/Neutron Diffraction

38

20

30

40

Ab-initio calculation will provide better understanding

of crystal structure

40
2

50

60

70

Objective
Calculation of local structure of
NBT using ab-initio method and
comparison with Raman and
XRD data

Structure modeling of
NBT
NBT constitutes a complex perovskite
structure with two different ions Na+ and Bi3+
occupy at A site.

Na 0.5 Bi 0.50

In R3c structure, we argued that two different

ions at A-site cant occupy the symmetrically
equivalent position. It suggests that the
structure should be lower that R3c.
Ti

Computational Details
First-principles calculations have been performed within the generalized gradient
approximation (GGA) using PW91 exchange-correlation functional to density
functional theory as implemented in CRYSTAL09 code.
Tight convergence criteria are used to obtain fully relaxed total energy
calculations.
We used following norm-conversing pseudo-potentials for Bi, Na , Ti and O.
Bi: 5d10 6s2 6p3,
Na:2p6 3s1, Ti: 3s2 3p6 4s2 3d2 and O:2s2 2p4
An 8x8x8 Monkhorst-Pack k-point mesh for the primitive cell is used for Brillouin
zone integration.
In all the calculation plane-wave energy cutoff is set to be 770 eV resulting in a
numerical error of less than 1meV/atom.

We converted the structure in P1 symmetry

and the resulting configuration is structurally
optimized. R3 or R3m structures are
obtained from the optimized structure.

In R3 structure

In R3m structure

Raman scattering intensities

Raman scattering is the inelastic scattering of photons. The monochromatic
laser light interacts with molecular vibrations (i.e. phonons), resulting in the
energy of the laser photons being shifted up or down. This shift of energy gives
crucial information about the vibrational modes in the system.

Using Raman intensity

calculation, it is possible to
identify the symmetry and
chemical structure of the system.

Calculation of Raman scattering

intensities of NBT in R3 and R3m
structures
1.2

R3

1.0

Intensity (arb. units)

Intensity (arb. units)

1.2

0.8
0.6
0.4
0.2
0.0

200

400

600

-1

Wavenumber (cm )

800

1000

R3m

1.0
0.8
0.6
0.4
0.2
0.0

200

400

600

800
-1

Wavenumber (cm )

Vibration modes exist between 80 930cm -1

1000

Calculation of Raman scattering intensities

for R3c structure
Intensity (arb. unit)

Na0.5Bi0.5TiO3

Na+ 0.5
Bi3+ 0.5

0.5x1+0.5x3=2

Ba2+ 1.0

For BiFeO3 having R3c symmetry

the vibration modes predicted
between 95 590cm-1
H. M. Ttnca and G. P. Srivastava, JAP, 1 03 (2008) 083712

100

200

300

400

500

Wavenumber (cm-1)

Vibration modes exist between 120 500cm -1

Raman spectrum of NBT

Intensity (arb. units)

24000

12000

0
150

300

450

600
-1

Wavenumber (cm )

750

900

Vibrational modes at higher

frequency

Bi-O bond length

2.273

In R3c structure Bi-O bond lengths all greater than 2.53 . However the
experimentally measured shortest bond length from EXAFS study is 2.2 .
Our calculated value of the shortest bond length (Bi-O=2.25 ) in R3 structure
is in good agreement with the experimental value.

Intensity (arb. units)

0.85NBT-0.15BiCrO3

18000

9000

0
150

300

450

600

750
-1

Wavenumber (cm )

900

Conclusion
Local

structure of NBT is R3/R3m or

lower symmetry.
The high frequency modes in Raman
spectrum are intrinsic feature of NBT.

Thank You