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K.Z. Rushchanskii a, H. Haeuseler b,*, D.M. Bercha c

a

Institute of Solid State Physics and Chemistry, Uzhgorod National University, 54 Voloshin Str., 88000 Uzhgorod, Ukraine b r Anorganische Chemie, Universita t Siegen, D-57068 Siegen, Germany Laboratorium fu c Institute of Physics, Pedagogical University, Rejtana 16a, 35-310 Rzeszow, Poland Received 4 September 2001; revised 3 January 2002; accepted 18 January 2002

Abstract For the compounds FeGa2S4 and NiGa2S4 band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals. q 2002 Published by Elsevier Science Ltd.

Keywords: A. Chalcogenides; C. Ab initio calculations; D. Defects; D. Magnetic properties

1. Introduction Compounds with layered structures are an attractive eld of basic and applied research because of their anisotropic physical properties and they nd applications in the development of photodetectors, switches and photovoltaic devices. Recently, semiconductors with a layered structure have been applied to manufacture heterojunctions because the peculiarities of their composition produce an ideal heterocontact. Due to the distinct asymmetry of chemical bonds in these compounds and the presence of boundaries of the neighbouring layers with saturated bonds, practically perfect surfaces without defects and undesired electric elds can be created. The presence of strong chemical bonds only between the atoms within a single slab permits to grow quality heterojunctions and superlattices in the direction of the weak bond by means of the so-called van der Waals epitaxy [1]. From this point of view, the layered semiconducting crystals belonging to the A IIIB VI group are particularly inter* Corresponding author. Fax: 149-271-740-2555. E-mail address: haeuseler@chemie.uni-siegen.de (H. Haeuseler).

esting in applications because some of them exhibit a wide range of non-linear optical, electrical and mechanical effects. Introduction of transition elements in these compounds would result furthermore in interesting magnetic properties. One group of layered materials which can contain transition elements is that of the ternary and quaternary chalcogenides crystallising in one of the polytypes of the ZnIn2S4 structure. Mainly two different structures are found among this group: FeGa2S4-type and ZnIn2S4(IIIa)-type. These compounds are known to be semiconductors with band gaps between 1 and 2 eV [2]. To our knowledge, there is no band structure calculation reported in the literature for this type of compounds. As most of the compounds crystallizing in one of the two structures show disorder of the metal atoms or vacancies and only FeGa2S4 and NiGa2S4 are well ordered [3,4] we decided to perform band structure calculations for these two compounds. It is interesting to note the similarity of the crystalline structure of these compounds with the structure of one of the most investigated layered compounds, GaS (a 358:7 pm; c 15:492 pm [5]) as can be seen from the only slightly smaller aparameter of GaS.

0022-3697/02/$ - see front matter q 2002 Published by Elsevier Science Ltd. PII: S 0022-369 7(02)00188-9

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Fig. 1. Crystal structure of the FeGa2S4-type perpendicular (a), and parallel (b) to the c-axis. Arrows denote the different sections shown in the charge density distribution pictures of Fig. 2. (c) Principal points and directions in hexagonal BZ.

2. The crystalline structure of FeGa2S4 and NiGa2S4 The structures of layered FeGa2S4 and NiGa2S4 crystals have been determined by Dogguy-Smiri et al. [3] and Lutz et al. [4], respectively. Both crystals belong to the hexagonal system described by the D3 3d space group with the basis vectors of the elementary cell: a 365:4 pm; c 1205:6 pm for FeGa2S4 and a 362:5 pm; c 1199:6 pm for NiGa2S4. The layer structure (Fig. 1) is built from slabs formed by four anion layers which are stacked in the direction of the c-axis. In the centre of these slabs there is a sheet of edge-sharing octahedra which are connected on both sides to sheets of corner-sharing tetrahedra by common corners. The elementary cell contains one formula unit, i.e. seven atoms, which form only one slab. Therefore the physical properties do not show any effects connected to Davydov splitting [6]. These layers with a complex structure are themselves bound to one another by weak van der Waals interactions with a so-called van der Waals gap between the slabs. The fractional co-ordinates for both compounds are compiled in Table 1. One of the three cations of the formula unit is octahedrally co-ordinated, i.e. Fe and Ni, and the

Table 1 Lattice parameters/pm, space group, and fractional co-ordinates of the a-FeGa2S4-type compounds FeGa2S4 and NiGa2S4 FeGa2S4 [3] Lattice parameter a Lattice parameter c SG MV Mt(1) S(1) S(2) 365.4 1205.6 m1 P3 0 0 1 2 1 2 3 3 .2092 1 2 3 3 .8694 1 2 3 3 .3927 NiGa2S4 [4] 362.5 1199.6 m1 P3 0 0 1 2 1 2 3 3 .2145 1 2 3 3 .8679 1 2 3 3 .3985

other two, i.e. Ga, tetrahedrally. The transition metal atoms are situated on the centre of inversion. The layer structure contains two symmetrical non-equivalent anions S1 and S2. One of these (S1) which forms the outer layer of the slab is covalently bound to Ga with a distance Ga S1 221.23 pm, which is comparable to the corresponding distances in GaS (233 pm) [5]. But contrary to these compounds, the gallium atoms do not form (Ga2)-clusters in FeGa2S4 and NiGa2S4 but are covalently bound to the anion S2 with a distance GaS2 231.26 pm which is 10 pm longer than GaS1. The reason for this difference can be found in the fact that the anions S2 have a coordination number 4 while for the anions S1 the coordination number is only 3. Furthermore, as Hulliger postulates [7] there is an interaction between Ga and S1 of the neighbouring slab leading to a shift of the gallium atoms from the centre of the tetrahedron to the outer border of the slab. The transition elements Fe and Ni which are located in the centre of the slab, are only co-ordinated by S2 atoms. The distance FeS2 247 pm is nearly equal to the distance resulting from the radii given by Shannon (250 pm) for Fe 21 in a high spin state [8].

3. Symmetry description and energy band structure in the empty-lattice approximation To obtain information on the symmetry aspects of the energy band structure, a group theoretical investigation in the empty-lattice approximation has been done. m 1 D 3 The symmorphic space group P3 3d contains 12 symmetry operations [9], which in a hexagonal basis are as follows: h1 x; y; z; h3 2y; x 2 y; z; h5 y 2 x; 2x; z; h7 2x; y 2 x; 2z; h9 x 2 y; 2y; 2z; h11 y; x; 2z; h13 2x; 2y; 2z; h15 y; y 2 x; 2z; h17 x 2 y; x; 2z; h19 x; x 2 y; z; h21 y 2 x; y; z; h23

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2y; 2x; z: High-symmetry points and directions in the Brillouine zone (BZ) are presented in Fig. 1c. In the highsymmetry points G and A there are six irreducible representations (G 1 G 6 and A1 A6), in points L and M four ones and in points H and K three (see Appendix A). The investigation of the spectra in the empty-lattice approximation shows for FeGa2S4 and NiGa2S4 that in the G point of the BZ there is the following order of the irreducible representations with increasing kinetic energy

G1; G1G4; G1G4; G1G4; G1G4G5G6; G1G1G4 # G4G5G5G6G6;

Table 2 Valence electron congurations used in the calculations Fe 4s 23d 6 Ni 4s 23d 8 Ga 4s 24p 1 S 3s 23p 4

4. Calculation details The band structure calculations were performed using the plane wave pseudo-potential method [20] based on densityfunctional theory [21]. We used non-local norm-conserving pseudo-potentials in the form of Kleinman and Bylander [22], calculated on the basis of the Hamman scheme [23] for Ga and S and on the basis of the TroullierMartins scheme [24] for the construction of the soft pseudo-potentials for the transition metal elements Fe and Ni. Both schemes are realized in the program package fhi98PP [25]. To take into account the exchangecorrelation interaction we used the general gradient approximation (GGA) in the form proposed by Perdew and Wang [26]. In Table 2 we present the valence electron congurations taken into account for the construction of the pseudopotentials. In Table 3 the cutoff radii rcl [23,25] for the respective components of pseudo-potentials of these atoms are given. Scalar-relativistic effects were included in the pseudo-potential. The parameters chosen by us assure generation of `ghostfree' pseudo-potentials in the terminology proposed by Gonze et al. [27]. The band structures of FeGa2S4 and NiGa2S4 were calculated by the means of the fhi98md program [28]. The wave functions were expanded in plane waves with a kinetic energy cutoff 60 Ry, which corresponds to approximately 7400 plane waves. To obtain the ground state of the electron system we used in our calculations the steepest descent algorithm [28]. We found this algorithm more stable in our computations than the Joannopoulos algorithm [28]. Integration in the k-space over the BZ was done by means of a special k-point method [29]. We used a mesh of the 8 8 4 k-points, which were reduced to the 72 special k-points in the irreducible part of the BZ. The effects of using a larger cutoff and a larger set of k-point on the calculated spectra are found to be insignicant.

Table 3 Cutoff radii (in Bohr) for the pseudopotentials of s, p, and d orbitals used in the calculations. Potentials, denoted by star are used as local potential [25] Fe s (l=0) p (l=1) d (l=2) 2.35 (*) 2.45 2.25 Ni 2.25 (*) 2.35 2.15 Ga 1.25 1.489 2.25 (*) S 0.77 1.08 1.08 (*)

(in this investigation we have considered the valence band without d-electrons of the transition atom elements, so this result is identical for both FeGa2S4 and NiGa2S4). The irreducible representations G 5 and G 6 are twofold degenerate. At the position marked by the arrow there should arise the energy gap when the pseudo-potential is included. To obtain a closed valence band separated from the conduction band by an energy gap we used compatibility conditions for the principal directions and the highsymmetry points in the BZ (see Appendix A). This investigation shows that the valence band is formed from the following set of states: 4G 1 ; G 4 1 2G 5 ; G 6 : We would like to discuss the concept of minimal band complexes in a band structure. First papers devoted to determining the formula units of energy spectra were published in the 60s and 70s [10,11]. Later Zak introduced a concept relating band representations and continuity chords to the Wyckoff positions in the Wigner-Seitz cell [12,13]. These works led to an extensive theory developed by Michel and Zak [15] (and references in this paper). Finally, the term `elementary energy bands' has been introduced [15]. However, before papers [12,13] have been published, the authors of Refs. [16,17] predicted a smallest formula unit of the energy spectrum of SbSI crystal. The topology of this unit reects the strong anisotropy of the crystals and the presence of translationally non-equivalent chains of atoms in its unit cell. Investigations of the band structure of the SbSI crystal by the semiempirical pseudo-potential method [18] conrmed these predictions. Some separate units of the energy spectrum, designated as the `minimal band complexes', are clearly visible in the band structure of the SbSI crystal. Unlike in Refs. [1115] the minimal band complexes were determined from calculations of a band structure in the empty-lattice approximation using the simplest data about a crystal. As was underlined in Ref. [19] the term elementary energy bands and the minimal band complexes are equivalent. In our case, the valence band is composed of two types of the elementary energy bands, described in the G point by the following representations: G 1 % G 4 and G 5 % G 6.

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Fig. 2. Calculated energy band structure of FeGa2S4. The energy of the top of the valence band is set to zero.

The chosen parameters also allowed to obtain an excellent convergence in the calculations. We did not take into account spinorbit interactions.

5. Results and discussion The electronic band structures of FeGa2S4 and NiGa2S4 are shown in Figs. 2 and 3, respectively, for the high-

symmetry directions in the rst BZ. In principle, the electron spectra of FeGa2S4 and NiGa2S4 are similar to those of aIn2Se3 [30]. That is not surprising as the layered structure of a-In2Se3 is very similar to the structure of the compounds under investigation: in both structures the chalcogenide ions form a hexagonal closed packed array with the trivalent metal ions (Ga and In, respectively) in tetrahedral sites. The main difference is found in the thickness of the slabs forming the layer structure due to the missing layer of the

Fig. 3. Calculated energy band structure of NiGa2S4. The energy of the top of the valence band is set to zero.

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Fig. 4. Valence chargedensity distribution for NiGa2S4 in different planes (compare Fig. 1). The maximal density is 0.26 a.u., the interval of the contour lines is 0.005 a.u. For the van der Waals gap (AA) the interval of the contour lines is 0.001 a.u.

transition elements in octahedral coordination in indiumselenide. Due to this similarity, both spectra exhibit nearly the same energy width of the valence band (,15 eV). In both cases two clearly separated valence bands are observed, the lower one connected to the s electrons of the chalcogenide ions and the higher one formed from the s electrons of the A III atoms and the p electrons of the chalcogenide ions. In our case the low energy part of the valence band contains four branches, which form two complexes of type G 1 % G 4 due to the presence of two symmetry inequivalent anion atoms (S1 and S2) in FeGa2S4 and NiGa2S4. The top of the valence band is found in the G point connected to the p-orbitals of the chalcogenide atoms, as will be discussed below. The bottom of the conduction band is equally localized on the G point for both considered crystals. This situation is very similar to the one found in aIn2Se3 [30]. But introduction of transition metal atoms in the A IIIB V matrix leads to specic interatomic interactions, which are mirrored in the energy band spectra. If in a compound containing transition elements, the distance between next nearest transition metal atoms is comparable to their distance in the metal, dd interaction have to be considered additional to the pd interaction between the anion and the transition element. If both interactions occur simultaneously, interesting physical properties may result as ferromagnetism, Fermi-glass behaviour, etc. Such a situation is observed in compounds of the type MM 0 4X8 [31] (M Ga, Al, M 0 Cr, V, Mo, X S, Se), in which tetrahedral clusters of transition elements M 0 are formed with M 0 M 0 distances comparable to the distances in the pure metal M 0 . In the compounds FeGa2S4 and NiGa2S4 the smallest distances between Fe and Ni atoms, respectively, are equal to the lattice parameters a and thus are much bigger than the interatomic distances in Fe (bcc, a 286:645 pm [32]) and Ni (fcc, a 352:38 pm [32]). We therefore do not expect strong interaction of the d-shells in these compounds but only interaction of the d-shells with the p-shells of the ligands, i.e. sulfur.

Fig. 4 shows the total valence charge density for NiGa2S4. As can be seen from the sections AA and FF there is no bonding between the layers. The main part of the valence electrons is concentrated on the anion atom orbitals. The sections CC and FF show that for both the sulfur atoms S1 and S2 the charge distribution is strongly deformed in the direction of the Ga-atoms pointing to a strong covalent character of bonding within the GaS network. The charge density deformation of the S2 atoms in the direction of the transition metal atoms on the other hand is not so strong. There is only a slight deformation in the direction of the transition element (section DD in Fig. 4). Furthermore the transition element is nearly spherical leading to the conclusion that the bonding between the octahedrally co-ordinated cation and the GaS framework is mainly ionic. The short interatomic distance GaS1 compared to the distance GaS2 is due to the stronger covalent bonding between Ga and S1 atoms which form the outer border of the slabs. The sulfur atoms S2 on the other hand participate in the more ionic bonding to the transition metal atoms. The charge density distribution in the van der Waals gap (section AA) is typical for the hexagonal closed packed arrangement of the anions around the van der Waals gap as can be seen from a comparison with GaS-like crystals. As is shown in section EE of Fig. 4, there is no interaction between the d-shells of neighbouring Fe or Ni atoms. In the presence of an octahedral crystal eld, the vefold degenerate 3d levels of transition elements split into triply degenerate t2g and doubly degenerate eg levels (in the terminology of atomic orbitals); the t2g group of orbitals consist of dxy, dyz and dzx orbitals, while the eg group consists of the dx 22y 2 and d3z 22r 2 atomic orbitals. This splitting between t2g and eg is expected to be further enhanced by the anisotropic interactions between the 3d-levels and the p-levels of the ligands. The t2g levels interact with the ligand p-levels via pdp interaction p forming a bonding (t2g)antibonding (t2g ) pair, while the eg levels interact with the ligand p-levels through pds hopping interactions, forming the bonding (eg)antibonding

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Fig. 5. Energy gap part of (a) FeGa2S4 and (b) NiGa2S4 electron spectra and the corresponding wave function distributions at the G point. Contour plots are in arbitrary units with 40 contour lines between maximum and minimum.

p (eg ) levels. Since the pds interaction is approximately p twice as large as the pdp one, the eg eg splitting is larger p than the t2g t2g splitting, enhancing the effective crystal eld splitting, as mentioned before. These local atomic p p orbitals corresponding to t2g, t2g , eg and eg are expected to mix between different atoms in a periodic solid via transition elementligand atomtransition element interactions, leading to the formation of the corresponding bands. 3 As in the crystal eld of space group D 3 d only states are allowed, which are twofold degenerate at maximum, for the delectrons only G 1 and 2G 5 states are possible. Two of these (G 1 and G 5) correspond in our case to the pseudo-t2g levels while the pseudo-eg levels are formed from G 5 states. In Figs. 2 and 3 we can observe clearly separated subbands, which nearly do not show any dispersion. For FeGa2S4 this subband is formed from G 1 and G 5 states with an energy of 0.86 eV for G 1 and of 1.08 eV for G 5. For NiGa2S4 on the other hand this subband is formed from branches, which in the G -point have G 1 and G 6 symmetry with an energy of 0 eV. To understand the difference between the symmetry descriptions in both cases we have investigated the wave function distribution for the corresponding levels at the G point (Fig. 5). These distributions show, that for FeGa2S4 the

considered subband is formed from strongly localised orbitals on the Fe atoms. This is consistent with the picture known from ligand eld theory that this band corresponds p to antibonding pseudo-t2g orbitals. The corresponding wave function distribution for NiGa2S4 on the other hand shows, that the G 1 level is formed from antibonding orbitals on Ni and S2 atoms and the twofold degenerate level with G 6 symmetry is formed from the wave functions of the porbitals of S2 atoms. Wave functions with G 5 symmetry strongly localised on Ni atoms form a level with an energy, which is approx. 0.22 eV deeper than the considered subbands G 1 and G 6. The same picture is observed for the A point, too. However, the distribution of wave functions, which correspond to the subband levels in the L, M, K and H high-symmetry points of the BZ point out to a strong localisation of orbitals on the Ni atoms. So, in these points p subband levels are correspondent to the pseudo-t2g orbitals. The different symmetries of these subbands in FeGa2S4 and NiGa2S4 may be interpreted in the following way. Strongly localised orbitals on the Ni atoms with G 1 and G 5 symmetry p form the pseudo-t2g subband. The subband G 1 has an energy, which is in principle nearly equal to that of the G 6 levels formed from p-orbitals of S2 atoms. Both G 5 and G 6 levels

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Fig. 6. Energy band structure of FeGa2S4 calculated with frozen d-shells for the transition element atom.

split into equivalent sets of states (T1 % T2) and (S 1 % S 2) in the corresponding directions T and S . Branches, which are connected with G 6, have an inverse parabolic dispersion, which is typical for the top of the valence band. Branches connected with G 5 levels are in principle non-disperse. As the difference between the G 5 and G 6 levels is only 0.22 eV this leads to a crossing of branches and correspondingly to a splitting and strong interaction of branches with the same symmetry in the neighbourhood of the G point (approx. for 0.2 kS and 0.2 kT). In the D direction both sets of branches corresponding to G 5 and G 6 levels are non-dispersive. So, in this direction we do not observe a crossing of the branches and the wave function localisation picture is conserved to the A point. If the origin of a system of co-ordinates for both crystals is chosen in the maximum of the valence band which is described by the representation G 6 then p the energy distance between the G 5 state of pseudo-tg orbitals in FeGa2S4 and NiGa2S4 crystals is equal to 1.30 eV. This quantity is comparable with the difference between the energy position of 3d electron free states of Fe and Ni atoms that is equal to 1.37 eV. We can conclude, that for NiGa2S4 the S2 orbitals are p more important in the formation of the pseudo-t2g subband compared to FeGa2S4. The dd interaction is very weak as can be seen from the corresponding wave function distribution and from the nearly at d-band. For both compounds, the width of p the t2g -band is smaller than 0.7 eV. p The G 5 subband, which corresponds to the pseudo-eg level in FeGa2S4, fully overlaps with the conduction band while for NiGa2S4 this band has only a small overlap (,0.2 eV) with the bottom of the conduction band. To estimate the dp interaction the band structure calculations have also been performed including the pseudo-potentials of the transition elements constructed with frozen d-shells (FDS). The results of these calculations (see Fig. 6) show nearly

no difference in the dispersion of the bands. The main differences are obtained in the vicinity of the band gap which is mainly connected to the S2 atoms. In the band structure, which is calculated without d-electrons, the top of the valence band is mainly formed by non-bonding pairs of p-orbitals of S2, which form the inner part of the slabs. This state has G 6 symmetry. With the neighbouring bands G 5 there is a strong interaction, connected with cross splitting of branches in R and S directions. This leads to a nearly at top valence band in A L M G directions. The bottom of the conduction band is localised in G -point and has G 1 symmetry. The next higher band is separated by ,0.5 eV and has G 4 symmetry. Both spectra for FeGa2S4 and NiGa2S4 crystals are nearly equivalent. This is connected with the in principle identical A IIIB VI matrix of these compounds. Small deviations in the lattice parameters are mirrored in small changes of some levels, which are connected to the p-shells of S2 atoms. These changes in energy positions are less than 0.5 eV. The energy band spectra calculated within the FDS-approximation point out, that the band gap is direct and localised in the centre of the BZ. The calculated width of the band gap is about 1.7 eV. Experimental values of the band gap energies of FeGa2S4 and NiGa2S4 are not available in the literature but for the compound MnGa2S4 which exhibits a similar, though monoclinic structure a value of E g 1:2 eV is reported [33] and for the wurtz-stannite Cu2ZnGeS4 where the structure is based as well on a hexagonal close packing of the sulde ions but with all cations in tetrahedral coordination, a value of 2.1 eV is given [34]. So the calculated band gap of 1.7 eV seems to be reasonable. Including the d-shell electrons of transition metals into the electron density self-consistent calculations leads to a d p interaction of these electrons with the p-electrons of S2 atoms. The formation of a dp interaction between these atoms is mirrored in an energy change of some levels. Maximal changes in comparison with FDS-results are

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obtained for a G 5-levels, which in FDS-spectra forms a valence level 2 nd from the top of the valence band. This level decreases in energy to ,2.89 eV for NiGa2S4 and ,2.16 for FeGa2S4 crystals and forms the bonding pseudo-eg levels. The bonding pseudo-t2g bands, which are constructed from levels with G 1 and G 5 symmetry, make a pdp interaction. The corresponding energy changes are small. Furthermore some small changes are observed for deep levels, which are due to s-orbitals of S2 atoms. In connection with these results, it is interesting to look for a connection between the band structure and the crystal structure. According to the concept of the `elementary energy band theory', which is mentioned in Section 3, the topology and symmetry of the bands is a reection of the Wyckoff positions in the Wigner-Seitz cell. In our case Fe and Ni occupy the Wyckoff position (b) (0,0,1/2c) while Ga and S are in the position (d) (1/3a, 2/3a, zc) and (2/3a, 1/3a,zc). Let us consider in the beginning the simplest variant, the calculation of the energy spectrum in the FDS approximation. Since the 4s shells of Fe and Ni are ionized, it can be expected that the Wyckoff position (b) will not effect the topology of the valence bands. According to Ref. [9] there are three variants of the band representations describing the elementary energy bands corresponding to the (d) position: 1. G 1 % G 4 A1 % A4 L1 % L4 M1 % M4 K3 H3 2. G 2 % G 3 A2 % A3 L2 % L3 M2 % M3 K3 H3 3. G 5 % G 6 A5 % A6 L1 % L2 % L3 % L4 M1 % M2 % M3 % M4 K1 % K2 % K3 H1 % H2 % H3 : The symmetry of the energy states in the high-symmetry points of the BZ indicate that the elementary energy bands (1) and (3) are realised in the energy spectrum of the crystals considered in the given approximation. This result agrees fully with the results obtained in the empty-lattice approximation (see Section 3). It should be noted, that though for both Wyckoff positions (c) and (d) the local symmetry is equally 3m, the band representations describing the elementary energy bands are different. For the position (c) they have the following form G 1 % G 4 A1 % A4 L1 % L4 M1 % M4 K1 % K2 H1 % H2 ; so they are different for points K and H. The result of our numerical calculations of the energy spectra of the compounds under investigation are in full agreement with the elementary energy bands resulting from the Wyckoff position d, thus showing once again the power of Zak's concept. Considering the case when d-electrons are involved in the formation of the energy bands we can see that the topology of bands related to Ga and S, is the same as that obtained in the FDS approximation. The additional bands corresponding to d-electrons are described by the two following elementary energy bands:

They correspond to the Wyckoff position (b) occupied as mentioned by Fe and Ni. In the case of the Fe compound the bands corresponding to the G 1 and G 5 levels are clearly separated while in the case of NiGa2S4 the G 5 level due to the Ni in Wyckoff position (b) is near to or even overlaps with the G 5 % G 6 complex due to the S in Wyckoff position (d). This results in a combination of the elementary energy bands and a splitting of the energy levels. The valence band of FeGa2S4 is formed from 38 electrons, which result in 19 bands. The d-shell of Fe atoms contains six electrons. In the case of a weak crystal eld, these electrons are redistributed over all ve levels corresponding to a high spin distribution [35]. In the case of NiGa2S4 crystal 40 electrons form the valence band and eight d-electrons of the Ni atoms are redistributed on ve levels, too. So, in both cases p pseudo-eg orbitals contain two electrons with uncoupled spins. p In fact, that pseudo-eg levels have an overlap with the conduction band levels, so we should expect that these compounds exhibit metallic behaviour. But strong localisation of the p pseudo-eg orbitals on the transition metal atoms results in an impossibility of a participation of d-electrons in conduction mechanism in the considered crystals.

6. Conclusion Energy band structure calculations have been performed for the layered compounds FeGa2S4 and NiGa2S4 with full symmetry description. The topology of the calculated energy bands fully agrees with the one predictable from the elementary energy bands concept. The top of the valence band and the bottom of the conduction band are formed from bonding and antibonding p-orbitals of the sulfur atoms with a band gap of about 1.7 eV at the centre of the BZ. Within the gap a narrow band is located built by the d-orbitals of the transition metal atoms. In the case of NiGa2S4 this d-band is close to the top of the valence band and strongly mixes with the sulfur p-band. From the charge density distribution, we conclude that the crystals are made up from a GaS framework with mainly covalent bonding to which the transition metal atoms are connected via mainly ionic interactions. As expected bonding over the van der Waals gap is very weak.

Acknowledgements K.Z.R is very grateful to the DAAD for nancial support and to Professor M. Schefer for his permission to utilize the fhi98md and fhi98PP computer program.

G 1 A4 L4 M1 K1 H1 G 5 A6 L2 % L4 M1 % M3 K3 H3 :

Appendix A Table 4

Table 4 Characters table and compatibility relations (a) G and A points in BZ Irreducible representation h1 A1 A2 A3 A4 A5 A6 1 1 1 1 2 2 h3, h5 1 1 1 1 21 21 h7, h9, h11 1 1 21 21 0 0 h13 1 21 1 21 2 22 h15, h17 1 21 1 21 21 1 h19, h21, h23 1 21 21 1 0 0 Compatibility relations T1, S 1, D 1 T2, S 2, D 2 T2, S 2, D 2 T1, S 1, D 1 T1 1 T2, S 1 1 S 2, D 3 T1 1 T2, S 1 1 S 2, D 3

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(b) L and M points in BZ Irreducible representation L1 L2 L3 L4 (c) K and H points in BZ Irreducible representation K1 K2 K3

h1 M1 M2 M3 M4 1 1 1 1

h7 1 1 21 21

h13 1 21 1 21

h19 1 21 21 1

S1 S2 S2 S1

h1 H1 H2 H3

h3, h5 1 1 2

2027

2028

K.Z. Rushchanskii et al. / Journal of Physics and Chemistry of Solids 63 (2002) 20192028 approaches to obtain the minimal complexes of bands and their manifestation in spectra of strongly anisotropic crystals, in: T. Lulek, B. Lulek, A. Wal (Eds.), Symmetry and Structural Properties of Condensed Matter, World Scientic, Singapore, 2001, pp. 376382. J. Ihm, A. Zunger, M.L. Cohen, Momentum-space formalism for the total energy of solids, J. Phys. C 12 (1979) 44094422. W. Kohn, L.J. Sham, Self-consistent equations including exchange and correlation effects, Phys. Rev. 140 (1965) A1133A1138. L. Kleinman, D.M. Bylander, Efcacious form for model pseudopotentials, Phys. Rev. Lett. 48 (1982) 14251428. D.R. Hamann, Generalized norm-conserving pseudopotentials, Phys. Rev. B 40 (1989) 29802987. N. Troullier, J.L. Martins, Efcient pseudopotentials for plane-wave calculations, Phys. Rev. B 43 (1991) 19932006. M. Fuchs, M. Schefer, Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory, Comp. Phys. Commun. 119 (1998) 67. J.P. Perdew, Y. Wang, Accurate and simple density functional for the electronic exchange energy: generalized gradient approximation gas correlation energy, Phys. Rev. B 33 (1986) 88008802. X. Gonze, R. Stumpf, M. Schefer, Analysis of separable potentials, Phys. Rev. B 44 (1991) 85038513. M. Bockstedte, A. Kley, J. Neugebauer, M. Schefer, Densityfunctional theory calculations for poly-atomic systems: electronic structure, static and elastic properties and ab initio molecular dynamics, Comput. Phys. Commun. 107 (1997) 187. H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13 (1976) 51885192. N. Narita, S. Nagai, S. Saito, K. Nakao, Band structure of layered semiconductor a-In2Se3 by the numerical-basis-set LCAO method, J. Phys. Soc. Jpn 64 (1995) 16221628. N. Shanthi, D.D. Sarma, Electronic structure of vacancy ordered spinels, GaMo4S8 and GaV4S8, from ab initio calculations, J. Solid State Chem. 148 (1999) 143149. J. Emsley, The Elements, Clarendon Press, Oxford, 1989. P.G. Rustamov, M.A. Guseinova, M.A. Alidzhanov, M.G. Safarov, Synthesis and study of manganese gallium sulde and manganese antimony sulde, Russ. J. Inorg. Mater. 12 (1976) 12181219. D.M. Schleich, A. Wold, Optical and electrical properties of quaternary chalcogenides, Mater. Res. Bull. 12 (1977) 111 114. P.A. Cox, The Electronic Structure and Chemistry of Solids, Oxford University Press, Oxford, 1991.

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