International Journal of Scientific Research in Knowledge (IJSRK), 1(8), pp. 245-253, 2013 Available online at http://www.ijsrpub.

com/ijsrk ISSN: 2322-4541; 2013 IJSRPUB http://dx.doi.org/10.12983/ijsrk-2013-p245-253

Full Length Research Paper Calculation of Lattice Parameters and Energy Band Structure and Density of States the -ZrNCl with Ab Initio
Khatereh Sarvazad*, Soroosh Zarghani
Department of Physics, Abadan Branch, Islamic Azad University, Abadan, Iran *Corresponding Author: khatereh.sarvazad@gmail.com
Received 18 April 2013; Accepted 29 June 2013

Abstract. In this article we will compute structural parameters, band structure and density of state for the - ZrNCl compound, based on the Density Functional Theory and the solution of the Kouhan-Sham equations. The calculations have been done through PWscf software. In this study, soft pseudopotentials have been used for this compound. The volume of -ZrNCl unit cell decreases by increase of pressure. The pressure may cause different effects from various directions on the bonds. By increasing the pressure, the amount of decrease in c constant is 1.3 more than of a constant and the reason is that -ZrNCl is an anistropical structure. Since the compressibility is low, it can be said this compound is very hard. The band structure shows that this compound is a semiconductor with an indirect bandgap of 2.75 eV. By the partial density of state, it is identified that the Nitrogen atom plays an important role in - ZrNCl properties and the electrons of P orbital in the N atoms are very effective. The calculations have a good correlation with the experimental results. Key words: density functional theory - structural parameters - pseudopotential - lattice constant - band structure-density of state.

1. INTRODUCTION Layered compounds have attracted a great deal of attention due to their structural flexibility and interesting physical properties including superconductivity. Zirconium nitride chloride have two forms: form low temperature with layered structure type FeOC1 and form high temperature with layer structure type CdBr2. The form is very resistant in humidity while the form which is considered in the research is stable even in the water. -ZrNCl has been found by Yamanaka in 1996 (Yamanaka, 1996). This compound is a special layered structure and is composed of structural slabs of {Cl Zr -NN Zr- Cl}. Three such slabs are stacked rhombohedrally along the c-axis to build the unit cell (Chen, 2001). -ZrNCl was prepared by the reaction of Zr (99.9%,325 mesh) with NH4CI(99.5%)at 650 0C for 30 min under the flow of NH3 gas(99.9,2050cm3/min). Obtained samples were purified by a chemical vapor transport method (Kawaji, 1997; Yamanaka, 1998). This composition is an n-type semiconductor with an activation energy of 50-60 meV and it has a band gap of 3.4 eV(Ohashi, 1989). Upon Li intercalation, the system turns into a metal and superconducting state at low temperatures. This is the first superconducting layered nitride (Taguchi, 2006; Takano, 2008). Figure (1) shows the crystal structure of -ZrNCl (Shamoto, 1998). According to

the studies, very few theoretically studies have been done on this material. In this paper, calculations are performed on the structural and electronic properties of the -ZrNCl composition which include computing the lattice parameters, equilibrium volume V0 ,total equilibrium energy E0, bulk module B0, its drive B0`, compressibility, band structure, and density of the states which later ,computation and comparing the results made by the other researcher will be studied.

Fig. 1: The crystal structure -ZrNCl

2. MATERIALS AND METHODS The calculations have been done by using pseudo potential method in the framework of Density Functional Theory. In this study the method of

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Sarvazad and Zarghani Calculation of Lattice Parameters and Energy Band Structure and Density of States the -ZrNCl with Ab Initio

instability (us-pp) was used, therefore, it is very important to determine the pseudopotential exactly. -ZrNCl has the trigonal structure with the space group R 3 m and the lattice constants that have been measured experimentally, are a=3.604 0A and c=27.672 0A and used in the calculations (Adelmann, 2000). The calculations have been done with or without considering spiny interactions. To implementation energy convergence program is considered that with 10 cycles. The kinetic energy cutting the electronic wave functional based on plane waves 40 ridberg are elected which a lattice of 12*12*14 k-mesh is created. 3. RESULTS AND DISCUSSION 3.1. Calculation of lattice parameters One of the most important parameters in the calculations is the lattice constant .It is experimentally

measured and is available; however, it should be calculated in order to be conically. After optimization k points and cut energy, there is need to draw an energy graph the lattice parameters and the smallest volume is obtained which is the optimum volume and regarding to the studied structure, the lattice parameters can be extracted. To do this, convergence eigenvalue of structure energy for the different parameters have been calculated. Due to being self-equations, we can calculate the amount of energy to arbitrary precision. Energy changes based on volume is given by Mvrnagan, s state equation; the minimum energy is obtained for this compound by using this equation. One of these results is shown in figure (2).

-150.68 -150.7 -150.72

energy(Ry)

-150.74 -150.76 -150.78 -150.8 -150.82 -150.84 -150.86 1400 1600 1800 2000 2200 2400 2600 2800 volum e((a.u)^3)

Fig. 2: Energy diagram in terms of volume -ZrNCl. Following these calculations, other parameters such as lattice constant, bulk module, derivate of the bulk module to the pressure and compressibility has been calculated. The results are given in table (1) and compared with the both experimental and theoretical data made by others. In this table a&c are lattice constants, V0 is optimum volume, B is bulk module, B` is derivative of bulk module, k is compressibility and Emin is the minimum energy. According to researches, very few studies have done on this compound and no theoretical results have been obtained. The result show considering spiny interactions have a little effect on the structural parameters and improves the volume. Compressibility is defined converse to the bulk module and the bulk module represents the stability of the crystal, in other words, the more module volume means the more crystal stability. Now we will study effect of pressure on -ZrNCl. The graph of dependency of volume on the pressure for the combination has been shown in figure (3). The graph clears that the volume of unit cell decreases by increasing pressure. Since the compressibility is low, it can be said this compound is very hard. Graph of lattice parameters changes of a/a0 and c/c0 based on the pressure were shown in figure (4). According to the figure the lattice parameters decreases by increasing pressure, and it also can be seen that the amount of decrease in c constant is 1.3 more than of a constant and the reason is that ZrNCl is anistropical structure and this is due to the difference in the type of bonds along with a,c.

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Table 1: The structural parameters calculated

The calculated parameters Regardless of the spin interactions 321.484 3.65915 27.7581 7.5859 131 5.24 7.63*10-3 -150.84005 In view of the interaction of spin Experimental results(Istomin, 1999) 311.38 3.604 27.672 7.6769 -

V0 ( A0 ) 3

321.486 3.65916 27.7586 7.5860 131 5.24 7.63*10-3 -150.84007

a( A 0 )

c( A 0 )

c/a
B(kbar)
B

K (kbar) 1 Emin ( Ry )

2180 2160 2140

V((a.u.)^3)

2120 2100 2080 2060 2040 2020 2000 0 2 4 6 P(kbar) 8 10 12 14

Fig. 3: Diagram of dependency of volume on the pressure -ZrNCl

1.005 1
a/a.,c/c.

Series1 Series2

0.995 0.99 0.985 0.98 0.975 0 2 4 6 8 P(kbar) 10

12

14

Fig. 4: Diagram of -ZrNCl lattice parameters changes based on the pressure

3.2. Band structure calculations Another important result that can be derived from simulation of crystal properties is the graph of band structure. Nature of the crystal whether it is metal or not, measure of energy gap, if there is and its type whether it is direct or not, also method of distribution

of the electron states in the different energies can be derived from this graph. Accordance of this graph to density curve of the states could be a reason to accuracy of the calculations. Structures of the energy band -ZrNCl along with different symmetric lines are shown in figure (5).

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Sarvazad and Zarghani Calculation of Lattice Parameters and Energy Band Structure and Density of States the -ZrNCl with Ab Initio

Energy

Fig. 5: Diagram structure of the energy band -ZrNCl regardless of the spin interactions.

In this curve Fermi energy is located in the coordinate system origin, as it is clear from the figure (5) the levels of energy did not cut the Fermi level .It shows that -ZrNCl compound has indirect band gap of 2.75 eV in the point of . Table (2) shows the calculated band structure of this method with other

methods. The structure of energy band of -ZrNCl combination regarding to spiny interaction shows that this spiny interaction has no effect on the structure and the calculated gap has a good agreement with other results.

Table2: Band gap compared with the results obtained by others

Band gap No interaction of spin The interaction of spin Experimental results(Ohashi, 1984) Experimental results(Ohashi, 1989) Theoretical results(Hase, 1999)

E g (eV )
Type of gap in point

2.75

2.75

3.4

1.6-2

indirect

indirect

3.3. Density of states Electron distribution in energy spectrum is described by density of states. Density of state diagram -ZrNCl

has been drawn based on energy at the range -10 eV to 10 eV in figure (6).

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state ) Dos eV

(eV ) energy
Fig. 6: The -ZrNCl total density of states diagram

In the density of state diagram, zero energy scale presents Fermi level that it has been shown with vertical line. As it is clear from figure, maximum of the density of states is expanded from -4.5 eV to 0eV and approximately density of states is zero from -4.5 eV to later. For more accurate investigation about different orbitals participation, partial density of state of atoms energy has been shown in the next figures. According to these figures, it can be seen that N atoms share to Zr and Cl is more in dos of all compound. Therefore it can be concluded that N atoms have a basic role to determine the electronic properties of -ZrNCl. In figure (7) dos share of each Zr atom orbitals were compared to each other. As it is clear from figure, in Fermi level, density of states s orbital in the Zr atom is almost zero. For d orbital N

(Ef) is about 3 state/eV and for p orbital is about 0.3state/eV. Dos share of s and p orbitals in the N atom are compared in figure (8), for s orbital of N atom, peaks of energy have been located in limits 1eV to 4eV. Density of states for s orbital in Fermi level is almost 0.1 state/eV. It shows that s orbital of N atom has a small role in compound properties determining. Energy peaks for P orbital in the N atom are almost expanded from -3eV to 0eV. The P orbital of Nitrogen atom has basic role in electronic properties of all compound -ZrNCl. The N(Ef) for p orbital of N atom is about 4.5 state/eV.

state ) Dos eV

(eV ) energy
(a)

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Sarvazad and Zarghani Calculation of Lattice Parameters and Energy Band Structure and Density of States the -ZrNCl with Ab Initio

state ) Dos eV

(eV ) energy
(b)

state ) Dos eV

(eV ) energy
(c)
Fig. 7: The zirconium partial density of states diagram for a) d orbitals b)s orbitals c)p orbitals

state ) eV

Dos

(eV ) energy
(a)

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International Journal of Scientific Research in Knowledge (IJSRK), 1(8), pp. 245-253, 2013

state ) eV

Dos

(eV ) energy
(b)
Fig. 8: The partial density of states diagram of nitrogen atom for a) s orbitals b) p orbitals

Curve of partial density of states of s and p orbitals for Cl atom is shown in figure (9). As it is clear from figure N (Ef) of s orbital of the chlorine atom is about 0.1state/eV. Therefore s electrons of Cl atom have little share in total density of state and it basically shows unoccupied states also the N(Ef) of p orbital of Cl atom is about 2.5 state/eV. The p orbital of Cl atom in fact has a greater role in the electronic properties of total compound. 4. CONCLUSION Calculation has been done by using Ab initio method and looking at spiny interaction and obtained structural parameter have good compatibility with experimental consequences. Obtained consequences

determine that spiny interaction has insignificant effect on structural parameters and the consequences are an emphasis on the more difficulty and less compressibility of -ZrNCl compound. According to compound band structure, it is distinguished that energy levels have not been cut fermi level, this expresses that -ZrNCl is a semiconductor with band gap of 2.75eV. By looking at to the partial density of states diagram, it is distinguished that N atoms have important role to determine electronic properties of ZrNCl. The partial density of state of N atom shows that s orbital of N atom has an insignificant role, and p orbital of Nitrogen atom has basic role in electronic properties of all compound -ZrNCl.

state ) eV

Dos

(eV ) energy
(a)

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Sarvazad and Zarghani Calculation of Lattice Parameters and Energy Band Structure and Density of States the -ZrNCl with Ab Initio

state ) Dos eV

(eV ) energy
(b)
Fig. 9: The partial density of states diagram of chlorine atom for a) s orbitals b) p orbitals

ACKNOWLEDGEMENT This article is adapted from the research projects Calculation of lattice parameters and energy band structure and density of states the -ZrNCl with Ab initio which is supported by Islamic Azad Universit (IAU), Abadan Branch-Iran. REFERENCES Adelmann P, Renker B, Schober H, Braden M, Fernandez-Diaz F (2000).Structural Study of Superconducting Li-doped beta-ZrNCl. J of Low Temp. Phys., 117: 449. Chen X, Koiwasaki T, Yamanaka S (2001).HighPressure Synthesis and Crystal Structures of MNCl (M=Zr and Hf). Hiroshima University, 739-8527. Hase I, Nishihara Y (1999). Electronic Band Structure of -ZrNCl-based nanotubes. Phys. Rev. B 60, 1573 Hase I, Nishihara Y (2000). Electronic Band Structure of -ZrNCl-based nanotubes. Physica B 281 & 282, 788. Istomin SY, Kohler J, Simon A (1999). High-Pressure Synthesis and Crystal Structures of -MNCl (M=Zr and Hf). Physica C, 319: 219-228. Kawaji H, Hotehama K, Yamanaka S (1997).Valenceband Photoemission Study of -ZrNCl and the Quasi-two-dimensional superconductor NaxZrNCl. Chem. Mater., 9: 2127.

Ohashi M, Nakano H, Yamanaka S, Hattori M (1989). Valence-band Photoemission Study of -ZrNCl and the Quasi-two-dimensional superconductor NaxZrNCl. Solid State Ionics, 33/32,97. Ohashi M, Yamanaka S, Hattori M (1989). Valenceband Photoemission Study of -ZrNCl and the Quasi-two-dimensional superconductor NaxZrNCl. Ceram, J., Soc. Jpn., 97: 1175. Ohashi M, Yamanaka S, Sumihara M, Hattori MJ (1984). Superconductivity of Alkali Metal Intercalated -Zirconium Nitride Chloride, AxZrNCl(A=Li,Na,K). Inclusion Phenom., 2: 289. Shamoto S, Kato T, Miyazaki Y, Ohoyama K, Ohashi M, Yamaguchi Y, Kajitani T (1998). Electronic Band Structure of -ZrNCl-based nanotubes. Physica C306, 7-14. Takano T (2008).Effects of Molecule Intercalation In The Layered Nitride LixZrNCl Superconductor. Phys. Rev. B77, 104518. Taguchi Y (2006).Optical Properties of Layered Superconductor LixZrNCl. Phys. Rev. Lett. 97,107001. Yamanaka S (1996). Isotope Effect In LixZrNCl Superconductors. Adv.Mater. 8,77. Yamanaka S, Hotehama K, Kawaji H (1998). HighPressure Synthesis and Crystal Structures of MNCl (M=Zr and Hf). Nature (London), 392, 580.

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Khatereh Sarvazad is faculty member of physics department of Islamic Azad University, Abadan Branch, Iran. She holds MSc in Physics from IAU, Khouzestan Science and Research Branch. She is interested in research on her educational field; she organized a research project in Physics field. She has written the present article based on her research projects findings on Energy Band Structure and Density of States. She wrote this manuscript as corresponding author with the assistant of Dr. Soroosh Zarghani.

Dr. Soroosh Zarghani is faculty member of Physics department of Islamic Azad University of Abadan, Iran. He holds MSc in Physics from Tehran Science and Research Branch. Iran. Then He was recruited by Islamic Azad University of Abadan, Iran as a course instructor in Physics department since 2007; and now he is student of physical occanography in University of Khoramshahr. He is interested in research on his educational field, he organized a research project in Physics area. He has written the present article based on his research projects findings on Calculation of lattice parameters and energy band structure and density of states the -ZrNCl with Ab initio. He wrote this manuscript with the assistant of Khatereh Sarvazad, faculty member of Physics department of Islamic Azad University of Abadan, Iran.

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