Fluorine doped in Cubic perovskite SrMnO3:

first- principles calculations

Abdalla A. Mohamed
Department of Sciences and technology
Faculty of Physics
Omdurman Islamic University
Omdurman-Sudan

ABSTRACT
We report first–principles density- functional calculations for
electronic structure and magnetic properties of parent compound SrMnO3
doped by fluorine atoms. The aim is the variations of the valence of
manganese in the parent compound and prediction of new electronic and
magnetic properties which is can be lead to electronic industries utilization.
Trans position is favorable for oxygen replacement by fluorine atoms. The
new compound SrMnO2F has a tetragonal perovskite crystal structure with
supercell 2x2x2 parameters a=8.440Å b=c=7.697 Å. SrMnO2F is predicted
to be Insulating compound, with G-type antiferromagnetic in the ground
state (minimum energy). Finally A new spin arrangement on Mn ions
resulted in polarization of electrons on F ions.

I. INTRODUCTION
Increasing technological demands make many theoretical and
experiment researches devoted for new material possessing electronics
industries values. In the last years, many theoretical and experiment
researches have been devoted to studying mixed-valent manganite R1−x
AxMnO3 (R = rare-earth ion; A= Ca, Sr, Ba). The activity surrounding the
CMR manganites has been mainly focused on A1–x MxMnO3 perovskites
where the variation of the Mn oxidation state is achieved by a hetero-valent
cation substitution (divalent M cation for lanthanide metal A). The interest
on these manganese oxides originates from the promise of technological
applications [1]. Most of the studies have concentrated on the cation-rich
region or on the effect of oxygen content and varying the oxygen isotope
mass content in ABO3 type perovskites [2, 3, 4, 5] and very little work has
been reported on the anion-rich region. Undoped strontium manganites
SrMnO3 itself is a rare example of a compound having both cubic and
hexagonal perovskite structures, The electronic structure and magnetic
properties of both cubic and hexagonal structures of SrMnO3 have been
systematically studied by Rune et al.[6]. Doped fluorine in Double
perovskite Sr2 Mn2O5 to give a new oxy fluoride Sr2Mn2O5-xF1+x called 225F
was prepared and investigated by A.M. Abakumov et al [7]. The aim of this
paper is to employ first- principle calculations to study the effect of
replacement of oxygen by fluorine on the structural, electrical and magnetic
properties. The resulting compound had a tetragonal perovskite like-
structure with supercell parameters a=8.440Å b=c=7.697 Å.

II. COMPUTATIONAL DETAILS

We performed a periodic structure calculations of a perfect and doped

cubic perovskite SrMnO3 within the framework of density functional theory

method [8] using CRYSTAL06 code [9] with the hybrid B3LYP exchange

correlation functionals which consists of the mixture of the non-local exact

Hartree-Fock exchange[10] and Generalized Gradient Approximation

(GGA) exchange functionals as proposed by Becke’s three parameter

method combined with the non-local correlation potential of Lee et al. [11],
that has been shown to provide a good description of transition metal oxide

compound band gaps [12]. CRYSTAL06 employs atom-centered Gaussian-

type function as basis sets. The basis sets used were all-electron sets on Mn

(86-411d41) [9], O (8-411-d1) [14] and F (7-311) [15]. A pseudopotential

basis set (HAYWSC-31(3d)) [16] was used for Sr to reduce the computer

resource needed. When we modeling substitution on SrMnO3, the

experimentally measured lattice constant a=3.8(2) Å [17] and space group

Pm3m (221) in all structures are employed.

III. RESULTS AND DISCUSSION

A. Crystal structure
The unit cell of the parent compound containing one formula unit 5
atoms as shown in figure1. Optimization of cell parameters was performed
for each of the parent SrMnO3 and doped compound SrMnO2F. For the
ferromagnetic states, our optimized structure had cell parameter of a =
3.98Å for the parent compound compared to experimental value of 3.80Å.
The antiferromagetic phase of this compound corresponds to that geometry
where each Mn ion is surrounded by six nearest neighboring Mn ion with
somehow opposite spin. To achieve this computationally, we must consider
a cell containing two nearest neighboring Mn ions and break all symmetry
relationship between them, so that they may carry opposite spin. To show
the antiferromagetic properties, therefore the unit cell was extended to 2x2x2
supercell containing 40 atoms as shown in figure 2, corresponding to cell
parameter of a = 7.60Å. Our optimized cell parameter for G-type
antiferromagnetic state were a=7.66 Å which is in good agreement with the
experimental cell parameter.

For SrMnO2F compound, we performed geometry optimization on a

supercell having a cell parameter a=7.6 Å with substitution of eight oxygen
atoms by 8 fluorine atoms. In this cell, the local environment of the Mn3+
ions is an octahedron of four oxides and two fluorides. We performed a
number of different arrangements of fluorine ions around the Mn ion, such
as Cis, Trans and some other randomly substituted of F − ions. All
supercells were charge neutral. Our optimized cell parameter were a= 8.37Å
b=c=7.73Å for ferromagnetic state, while for G-type antiferromagnetic, the
cell parameter had a value of a=8.440Å b=c=7.697 Å i.e. a tetragonal crystal
structure is found and Trans position is a favorable position for fluorine ions
as depicted in figure 3.

B. MAGNETISM
The structural stability of cubic SrMnO3 is investigated by calculating
its total energy in ferromagnetic (FM) states and antiferromagnetic (AFM)
states. For the parent compound The G-type AFM (G-AFM) configuration
has the lowest energy and is assumed as the ground state, which is in
agreement with the previous experimental studies where G-AFM is
considered to be the ground state of cubic SrMnO3 [17]. For the fluorine F -
doped compounds, SrMnO2F, the G-AFM state was found also to be that of
lowest energy. The unpaired spin density (Mulliken α –β) on Mn for
SrMno2F was found to be (3.73) indicative of high spin of Trivalent
manganese Mn3+ (d4). For SrMnO3 was lesser (2.81). In both the above
systems there was no spin polarization of electrons on the anions. Figure 4
shown a new spin order distribution on Mn of the compound SrMnO2F
which gave rise to spin polarization of electrons on F, giving a small
unpaired spin density per fluorine atom of (0.06), and of (3.75) per
manganese atom and there was no spin polarization of electrons on O.

For ferromagnetic cases, in SrMnO2F, the unpaired spin density on

Mn (α –β) ions was found to be (3.84), and a small polarization on the oxide
ions (0.05) and for F ions there was increased spin polarization (α –β) =
0.07. In the case of the parent compound SrMnO3, it was found that the
unpaired spin density on Mn and O ions are 3.9 and 0.367 respectively for
the case of up and down spin of ferromagnetic case.

For SrMnO2F compound Although there is spin polarization of

electrons on fluorine ions in an antiferromagnetic state resulting from the
newly depicted spin arrangements as that shown in figure 4, polarization of
electrons on oxygen and fluorine in ferromagnetic state is greater than that
of the antiferromagnetic state. And it is greater for the ferromagnetic case of
the parent compound SrMnO3.

C. BAND STRUCTURE
For the parent compound SrMnO3, the figure 5a and 5b shows the
band structure and the total density of state DOS respectively for the
ferromagnetic case. In these case both of alpha and beta electrons graphs
crossing Fermi level indicating the possibility of a metallic state. The
calculations of G-type antiferromagnetic case of parent compound reveal an
insulating state at the level of minimum energy, the ground state. Figure 6a
and 6b shows the band structure density of states respectively.

For doped compound SrMnO2F the band structure and density of state
graphs shows that these compound is an insulating compound as Figure 7a
and 7b respectively. Concerning the SrMnO2F in which the fluorine ions has
electron polarization the band structure and density of state in this case are
slightly different from the case of G-type SrMnO2F compound. These
picture depicted in figure 8a and 8b respectively.

IV. CONCLUSIONS

In this paper, we reported the results of first- principles calculations

for parent cubic perovskite compound SrMnO3which doped by fluorine
atoms. The crystal structure of fluorine substituted SrMnO3 compound
calculations show that in its ground state a tetragonal perovskite structure
has been obtained. The lattice supercell 2x2x2 parameters a=8.440Å
b=c=7.697 Å. The lattice parameters and unit cell volume increase with
fluorine doping. The calculations show the case of fluorine substitutes for
oxygen; the Trans positions are favorable with respect to manganese ions.
The density of state and band structure shows insulating material in its
minimum energy level.

Acknowledgements

I would like to thank CRYSTAL support team -Torino for providing me a

free copy of CRYSTAL06 package through Dr E. A. Moore, Department of
Chemistry and Analytical Sciences- The Open University- Milton Keynes-
United Kingdom.
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Figure1: a 5 atoms SrMnO3 unit cell
Figure2: 40 atoms SrMnO3 2x2x2 supercell
Figure 3: SrMnO2F tetragonal crystal structure with F ions has a Trans position
Figure 4: spin order distribution on Mn for polarization of electrons on F ions
 Figure 5a: band structure of parent compound in ferromagnetic states where the alpha
band structure indicating the metal.
Figure 5b: DOS for ferromagnetic state of the parent compound SrMnO3
Figure6a: band structure of G-type ground state of SrMnO3 compound.
Figure 6b: Dos of insulating G-type antiferromagnetic of SrMnO3 compound.
Figure 7a: band structure of SrMnO2F compound
Figure 7b: total DOS of SrMnO2F compound.
 Figure 8a: the insulating state of SrMnO2F in which fluorine ions has electrons
polarization.
Figure 8b: density of state of SrMnO2F in which fluorine ions has polarized electrons.