Solid State Communications 334–335 (2021) 114361

Contents lists available at ScienceDirect

Solid State Communications

journal homepage: www.elsevier.com/locate/ssc

Changes in the physical properties of Mg2Ir3Si compared to Li2IrSi3 due to

the substitution of Li by Mg and the exchange of positions between Ir and Si
U. Jasia a, M.A. Alam a, *, M.A.H. Shah b, M.A. Hadi c
a
Department of Physics, Mawlana Bhashani Science and Technology University, Santosh, Tangail, 1902, Bangladesh
b
Department of Physics, Rajshahi University of Engineering and Technology, Rajshahi, 6204, Bangladesh
c
Department of Physics, University of Rajshahi, Rajshahi, 6205, Bangladesh

A R T I C L E I N F O A B S T R A C T

Communicated by Y.E. Lozovik The plane wave pseudopotential ab-initio method within the generalized gradient approximation (GGA) is
applied to investigate the structural, electronic, elastic, mechanical and optical properties including anisotropic
Keywords: factors, theoretical hardness, bonding nature of newly synthesized ternary silicide superconductor Mg2Ir3Si for
Silicide superconductor the first time. The optimized lattice parameters are in good agreement with the experimental values. The ob­
Density functional theory
tained results for Mg2Ir3Si are compared with the investigated as well as the available experimental and theo­
Mechanical properties
retical results of isostructural silicide Li2IrSi3. This study sheds light on the important effect of replacement of Li
Optical properties
by Mg and interchanging the atomic position of Ir and Si in the structure. The new compound is mechanically
stable and ductile in nature. Electronic band structures and density of states reveal that this compound has
complex bonding nature with partial metallic, covalent and ionic characters. The Vickers hardness is calculated
to be 2.85 and 6.81 GPa for Mg2Ir3Si and Li2IrSi3 silicide, respectively. Finally, various optical parameters such as
dielectric constant, refractive index, absorption coefficient, energy loss function, reflectivity, optical conductivity
are discussed with implications. The outcomes of this study assess the potential of the titled compounds as
absorbent and coating materials.

1. Introduction between electrons is mediated by lattice vibrations (phonons) and the

so-called Cooper pairs are formed [5]. Very recently, a new ternary
A silicide is a compound that consists of silicon (Si) with other ele­ superconductor Mg2Ir3Si with transition temperature of 7 K has been
ments which are relatively more electropositive than Si. Depending on discovered by Kudo et al. [2]. A conventional solid-state reaction pro­
how many types of elements present in the silicides, they can be divided cedure was used to synthesize Mg2Ir3Si. X-ray diffraction studies
into binary and ternary silicides. No binary silicides contain transition revealed that Mg2Ir3Si crystallizes in the hexagonal Mg2Cu3Si-type
metals and exhibit superconducting transition, while ternary silicides structure having space group P63/mmc, with Schönflies notation D6h4
contain 3d transition elements, and some of them show superconducting (No. 194) [6]. The structure of Mg2Ir3Si consists of Ir–Ir triangles con­
transition. From such point of view, the ternary silicides have grown nected by Si atoms. On the other hand, Li2IrSi3 consists of Si–Si triangles
renewed interest compared to binary silicides. Because of analogous connected by Ir atoms. In Mg2Ir3Si and Li2IrSi3 the positions of Ir and Si
electronegativity between transition metal and silicon, transition metals atoms are interchanged and Li+ was replaced with Mg2+ in the new
have a tendency to form a strong covalent bond with silicon [1]. How­ compound.
ever, the recent synthesis of ternary silicide superconductors Mg2Ir3Si In this study, we aim to explore the structural, electronic, elastic,
[2], Li2IrSi3 [1,3] and Li2PtSi3 [1,3], and prediction of Li2RhSi3 [4], mechanical and optical properties of the newly synthesized transition
Li2OsSi3 [4] are examples of renewed interest. The study of such ma­ metal silicide superconductor Mg2Ir3Si for the first time. The obtained
terials could pave the way for the possibility of obtaining the high results are compared with those either found in literature [1,3,7] or
temperature superconducting materials, where covalent characters of investigated in this study for Li2IrSi3. This study also sheds light on the
atomic bonding can play an important role for phonon-mediated su­ effect of replacement of Li ion by Mg and exchanging the position of Ir
perconductors [1]. According to BCS theory, an effective attraction and Si atoms in the structure of Mg2Ir3Si compared to Li2IrSi3 silicide.

* Corresponding author.
E-mail address: ashraf.rubd@gmail.com (M.A. Alam).

https://doi.org/10.1016/j.ssc.2021.114361
Received 27 March 2021; Received in revised form 3 May 2021; Accepted 4 May 2021
Available online 11 May 2021
0038-1098/© 2021 Elsevier Ltd. All rights reserved.
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

2. Calculation methods 3.2. Electronic structure

The density functional theory (DFT) calculations were carried out by In order to understand the nature of chemical bonding, we have
Cambridge Serial Total Energy Package (CASTEP) code [8]. In this studied the electronic band structures of Mg2Ir3Si and Li2IrSi3, and
calculation, we have employed plane wave pseudopotential approxi­ depicted in Fig. 2, in which the energy bands spread along high sym­
mation. Generalized gradient approximation (GGA) with PBE parame­ metry directions. The horizontal dashed line denotes the Fermi level
terization was considered for evaluation of exchange correlation (EF). It is observed that the number of energy bands increases in both
potentials. The ion-electron interactions were modeled by using valence and conduction bands of Mg2Ir3Si due to replacement of Li ion
Vanderbilt-type ultrasoft pseudopotentials [9]. The crystal structure was by Mg ion and interchanging the position of Ir and Si atoms relative to
fully relaxed using the Broyden–Fletcher–Goldfrab–Shanno (BFGS) al­ Li2IrSi3. In Mg2Ir3Si, the valence bands condense towards the Fermi
gorithm [10]. A k-point mesh of 5×5×4 grid within Monkhorst–Pack level and conduction bands expand towards higher energy region.
scheme is employed for Brillouin zone sampling [11] and a cut off en­ Consequently, the number of valence band crossing the Fermi level in­
ergy of 380 eV was considered for expanding the plane wave basis sets. creases. From the band structures it is clearly perceived that there is no
The convergence tolerance used for geometry optimization of the unit band gap between the valence bands and conduction bands, indicating
cell was: difference in the total energy within 5×10− 6 eV/atom; the metallic nature of Mg2Ir3Si and Li2IrSi3. The band structure modifies
maximum force within 0.01 eV/Å; maximum stress within 0.02 GPa; significantly when Li ion is substituted by Mg ion, and Ir and Si atoms
maximum ionic displacement within 0.005 Å and self-consistence field exchange their positions in the structure of Li2IrSi3. The number of
tolerance within 5×10− 7 eV/atom. bands crossing the Fermi level is three for Mg2Ir3Si, while the number of
bands crossing is two for Li2IrSi3. Therefore, Mg2Ir3Si is expected to be
3. Results and discussion more conductive than Li2IrSi3.
The total and partial densities of states (TDOS and PDOS) are studied
3.1. Structural properties to understand in depth the nature of the chemical bonding and are
shown in Fig. 3. It is evident that the substitution of Li ion by Mg ion and
The optimized crystal structure of Mg2Ir3Si is depicted in Fig. 1. exchange of position between Ir and Si atoms leads to increase in TDOS
Mg2Ir3Si crystallizes in the hexagonal structure with space group P63/ at EF in Mg2Ir3Si and modification in DOS profile relative to Li2IrSi3.
mmc. The unit cell consists of twelve atoms with two formula units. The TDOS at EF is found to be 7.84 states per eV per unit cell for Mg2Ir3Si,
Wyckoff position of Mg in Mg2Ir3Si is the same of Li in Li2IrSi3 as 4f with while for Li2IrSi3 this value is 2.91 states per eV per unit cell. The values
the fractional coordinates (1/3, 2/3, z). Meanwhile, the Wyckoff posi­ of non-zero TDOS at EF again confirm the metallic nature of Mg2Ir3Si and
tion of Ir in Mg2Ir3Si is 6h with coordinates (0.17013, 0.34025, 1/4), Li2IrSi3 that agrees with the band structure calculations and the previous
whereas Ir in Li2IrSi3 occupies 2a atomic site with (0, 0, 0). And the work [1,2,7] as well. The higher TDOS at EF may be responsible for
Wyckoff position of Si in Mg2Ir3Si is 2a with the fractional coordinates higher Tc of Mg2Ir3Si (7 K) compared to Li2IrSi3 (3.7 K). The main
(0, 0, 0), while Si in Li2IrSi3 resides at 6h atomic sites with the co­ contribution to TDOS at EF comes from Ir d states in Mg2Ir3Si and from Si
ordinates (0.34291, 0.17145, 1/4). It is clear that the Ir and Si atoms in p states in Li2IrSi3. Therefore, Ir d states contribute almost half of Si p
the Mg2Ir3Si exchange their positions relative to the position of the same states in TDOS at EF in Li2IrSi3. Additional p states of Mg (Li has only s
atoms in Li2IrSi3. states) plays important role in modification of electronic structure of
The calculated structural parameters are listed in Table 1 along with Mg2Ir3Si.
the experimental and theoretical data found in literatures for compari­ The valence band of both compounds consists of two parts. The lower
son. It is evident from Table 1 that the present results are in good valence band of Mg2Ir3Si extends from − 10.88 eV to − 8.48 eV while
agreement with the experimental values. The unit cell parameters a and Li2IrSi3 extends from − 12.75 eV to − 8.38 eV. It is to be mentioned that
c of Mg2Ir3Si, obtained in the present calculations, deviated from the lower valence bands of both Mg2Ir3Si and Li2IrSi3 arise due to hybridi­
experimental values [2] by 1.31% and 0.27%, respectively. The substi­ zation between Ir s and Si s orbitals, indicating covalent Ir–Si bonds. The
tution of Li ion by Mg ion and the exchange the position of Ir and Si covalent Ir–Si bond in Mg2Ir3Si is stronger than that of Li2IrSi3 because
atoms relative to Li2IrSi3 increase the lattice parameter a and reduce the the valance band of Mg2Ir3Si is in a deeper energy position. The upper
lattice constant c for new compound Mg2Ir3Si, and consequently in­ valence band of both compounds mainly consists of Ir d states. Some
crease the cell volume V. contribution comes from Si p and Mg s, p states in the case of Mg2Ir3Si
and from Si s, p and Li s orbitals in the case of Li2IrSi3 compound.

3.3. Elastic properties

A hexagonal crystal has six different elastic coefficients Cij (namely

C11, C12, C13, C33, C44 and C66), and five of them are independent since
C66 = 12 (C11 − C12 ). The evaluated single-crystal elastic constants are
listed in Table 2. According to born stability criteria [12], both Mg2Ir3Si
and Li2IrSi3 silicide are mechanically stable. It is to be mentioned that
large values of C11 and C33 indicate the strong bonding among the
constituent atoms in Mg2Ir3Si than Li2IrSi3 silicide.
The computed polycrystalline elastic constants, i.e., bulk modulus,
shear modulus and Young’s modulus are also tabulated in Table 2. The
bulk modulus B plays a vital role in resisting deformation of a com­
pound. Large value of B for Mg2Ir3Si indicates its high resistance to
deformation in comparison to Li2IrSi3. On the other hand, shear
modulus G is a measure of the resistance to shape change in solids. The
higher the shear modulus, the higher the rigidity of the material is. It is
observed that B is greater than G, indicating that the mechanical sta­
Fig. 1. Crystal structure of Mg2Ir3Si: 2D view (left) and 3D view (right). bility is governed by shear modulus. Young’s modulus Y is used to

2
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

Table 1
Equilibrium lattice parameters (a and c in Å), hexagonal ratio (c/a), internal parameter (z) and unit cell volume (V in Å3) for Mg2Ir3Si in comparison to Li2IrSi3 silicide
together with the available data.
Compounds Methods a c c/a z V Remarks

Mg2Ir3Si GGA 5.4179 7.4196 1.3695 0.5813 (Mg) 188.62 This work
Expt. 5.3530 7.4365 1.3892 0.5813 (Mg) – [2]
Li2IrSi3 Expt. 5.0176 7.8402 1.5625 0.5604 (Li) 170.94 [1]
Expt. 5.0139 7.8397 1.5636 0.0589 (Li) – [3]
GGA 5.0826 7.8600 1.5465 0.5663 (Li) 175.84 [7]

Fig. 2. Electronic band structures of (a) Mg2Ir3Si and (b) Li2IrSi3 along high symmetry directions.

Fig. 3. Total and partial DOS of (a) Mg2Ir3Si and (b) Li2IrSi3. The vertical dashed lines indicate the Fermi level (EF).

provide a measure of stiffness of solid material, i.e., the larger the value compared to Li2IrSi3.
of Y, the stiffer the material. Comparing all the moduli, it can be pro­ The Pugh’s ratio can provide valuable information regarding me­
nounced that the mechanical strength is higher in Mg2Ir3Si silicide chanical behavior of solids. This parameter is defined as the ratio of

3
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

Table 2
Calculated single-crystal elastic constants (Cij in GPa) and polycrystalline bulk modulus (B in GPa), shear modulus (G in GPa), Young’s modulus (Y in GPa), Pugh’s ratio
(G/B) and Poisson’s ratio (ν) for Mg2Ir3Si and Li2IrSi3.
Compounds C11 C12 C13 C33 C44 B G Y G/B ν Remarks

Mg2Ir3Si 312.4 166.4 105.6 309.5 50.3 187.1 68.8 183.8 0.368 0.34 This work
Li2IrSi3 198 71 55 295 68 116 72 179 0.62 0.24 [2]

shear modulus to bulk modulus (G/B) [13]. The threshold value of the We now concentrate on the anisotropy of the linear bulk modulus
Pugh’s ratio is 0.57 for separating the brittle materials from ductile ones. considering the bulk modulus Ba and Bc along the a and c crystallo­
If G/B > 0.57, the material is brittle in nature, otherwise the material is graphic axes, respectively, which can be defined as [15]:
ductile. The estimated G/B values are 0.368 and 0.62 for Mg2Ir3Si and
dP Λ
Li2IrSi3, respectively, indicating the ductile nature of Mg2Ir3Si and Ba = a = (7)
da 2 + α
brittle nature of Li2IrSi3. Poisson’s ratio ν [14] is another important
parameter to understand the mechanical behavior of a material. A fully dP Ba
metallic compound is characterized with the Poisson’s ratio of 0.33, Bc = c = (8)
dc α
while a completely covalent material has the Poisson’s ratio of 0.10.
Therefore, Mg2Ir3Si is expected to be more metallic than Li2IrSi3 (cf. where, Λ = 2(C11 + C12 ) + 4C13 α + C33 α2 andα =
Table 2). The metallic properties increase significantly when Li ion is (C11 + C12 − 2C13 )/(C33 − C13 )
substituted by Mg ion and Ir and Si atoms exchange their positions in the The estimated directional bulk modulus Ba and Bc is tabulated in
structure of Li2IrSi3. Table 3. The amount of deviation of these moduli from unity refers the
Now, we turn our attention to understand the elastic anisotropy of degree of elastic anisotropy possessed by the crystal. It is noteworthy
materials which impacts many physical properties such as internal that both Ba and Bc are larger for Mg2Ir3Si in comparison to Li2IrSi3
friction, phase transformation, elastic instability, mechanical yield silicide.
points etc. Firstly, the shear anisotropy of materials can be estimated by The machinability index, μM = B/C44, can be interpreted as a mea­
three independent factors (A1, A2, A3) for {100}, {010} and {001} shear sure of plasticity of materials [16]. The larger value of μM signifies the
planes, which can be defined as follows [15]: higher machinability of the compound; therefore, Mg2Ir3Si is easily
machinable than Li2IrSi3. The value of Cauchy pressure (CP = C12–C44) is
C11 + C12 + 2C33 − 4C13
A1 = (1) used to describe the brittle/ductile behavior and the nature of bonding
6C44
at the atomic level of a compound [17]. The positive value of CP in­
2C44 dicates the metallic bonding and ductile nature, while the negative value
A2 = (2) indicates the covalent bonding and brittle nature. The calculated values
C11 − C12
of μM and CP are listed in Table 3. Both Mg2Ir3Si and Li2IrSi3 have
C11 + C12 + 2C33 − 4C13 positive value for CP, indicating their metallic and ductile nature. For
A3 = (3)
3(C11 − C12 ) hexagonal symmetry, another class of anisotropy factor known as the
compressibility anisotropy factor which is defined as kc/ka, where kc is
For isotropic materials Ai (i = 1, 2 and 3) are equal to unity. Any
linear compressibility coefficient along c-axis and ka along a-axis, and
deviation of Ai from unity quantifies the shear anisotropy levels in ma­
expressed as [18]:
terials. We have also calculated the percentage of anisotropy in
compression (AB) and shear (AG), and universal anisotropy index (AU) kc C11 + C12 − 2C13
= (9)
using the following equations [15]: ka C33 − C13

BV − BR The calculated values of kc/ka for Mg2Ir3Si and Li2IrSi3 are found to
AB = × 100% (4)
BV + BR be 1.312 and 0.662, respectively (cf. Table 3) suggests that the linear
compressibility along c-axis is higher than that along a-axis for Mg2Ir3Si,
GV − GR whereas the linear compressibility along c-axis is lower than that along
AG = × 100% (5)
GV + GR a-axis for Li2IrSi3.

GV BV
AU = 5 + − 6≥0 (6)
GR BR 3.4. Mulliken populations and theoretical hardness

The subscripts V and R represent the Voigt and Reuss bounds,

Mulliken atomic population analysis provides more insightful in­
respectively. The zero values of these factors indicate the isotropic na­
formation to understand the nature of chemical bonding in solids [19].
ture and the increase in value from zero indicates the increasing level of
The Mulliken atomic populations calculated for Mg2Ir3Si and Li2IrSi3 are
anisotropy. In view of Table 3, it is evident that AB is higher for Li2IrSi3
listed in Table 4. From Table 4 we can see that Mg/Li and Si atoms carry
and AG is higher for Mg2Ir3Si silicide. Moreover, the anisotropy in shear
the positive charges and Ir atom carries the negative charges, indicating
is prominent than that of compressibility in both silicides. Universal
charge transfer from Mg/Li to Ir and Si to Ir atom. The value of overlap
anisotropy index measures the overall anisotropy level in materials, and
population close to zero implies that the interaction between the elec­
according to this index, Mg2Ir3Si is elastically more anisotropic than
tronic populations of the two atoms is negligible and consequently the
Li2IrSi3.
bond is remarkably weak, which can be ignored in the hardness

Table 3
Shear anisotropic factors (Ai), percentage anisotropic factors (AB and AG), universal anisotropic index (AU), linear bulk modulus (Ba and Bc in GPa), machinability index
(μM), Cauchy pressure (CP in GPa) and compressibility anisotropic factor (kc/ka) for Mg2Ir3Si silicide along with Li2IrSi3.
Compounds A1 A2 A3 AB AG AU Ba Bc μM CP kc/ka

Mg2Ir3Si 2.238 0.689 1.542 0.347 4.506 0.479 615.1 473.2 3.718 116.1 1.312
Li2IrSi3 1.566 1.070 1.677 0.862 2.778 0.303 305.4 461.0 1.705 3.0 0.662

4
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

Table 4
Mulliken atomic populations of Mg2Ir3Si silicide along with Li2IrSi3.
Compounds Species Mulliken atomic populations Remarks

s p d Total Charge (e)

Mg2Ir3Si Mg 0.49 6.58 0.00 7.07 0.93 This work

Ir 0.81 0.88 7.99 9.68 − 0.68
Si 1.24 2.59 0.00 3.84 0.16
Li2IrSi3 Li 1.99 0.00 0.00 1.99 1.01 [20]
Ir 0.77 1.31 8.26 10.33 − 1.33
Si 1.37 2.86 0.00 4.23 − 0.23

calculations. A small overlap population is an indication of a higher Fig. 4(a) it is also clear that these compounds are optically anisotropic.
degree of ionicity, whereas a high value emphasizes a higher degree of The large negative value of ϵ1(ω) indicates the Drude-like behavior as
covalency in the chemical bond. The Ir–Si bond in Mg2Ir3Si is only co­ seen in metals. It is observed that ϵ1(ω) becomes zero at around 25 eV,
valent bond with bond population of 0.38. On the other hand, Li2IrSi3 which corresponds to the energy at which the absorption coefficients
has two covalent bonds Ir–Si and Si–Si with bond population of 0.33 and vanishes (Fig. 4(e)), reflectivity exhibits a sharp drop (Fig. 4(g)) and the
0.56, respectively. It follows from Table 5 that Si–Ir bond is more co­ energy loss function (Fig. 4(f)) shows a sharp peak. Moreover, Fig. 4(a)
valent in Mg2Ir3Si than that in Li2IrSi3. Therefore, Li2IrSi3 is more co­ exhibits that the real part of the dielectric function goes through zero
valent than Mg2Ir3Si, and conversely, Mg2Ir3Si is readily machinable from below and the imaginary part of the dielectric function approaches
than Li2IrSi3. zero from above, which indicate that these compounds are metallic in
The knowledge of material’s hardness is very important for selecting nature.
the appropriate field of applications. Gou et al. [21] formulated an The real part of refractive index (n) represents phase velocity while
equation for estimating the hardness, which is expressed as: the imaginary part often termed as extinction coefficient (k) and it in­
∑ μ dicates the absorption loss of the electromagnetic wave when passes
( μ )nμ ] /
[∏ 1 n
through a media. In spite of some variation in height and position of
μ
Hv = Hv (10)
peak the overall features of refractive indices (real and imaginary) are
( )− same within the considered photon energy ranges. The refractive index
(11)
5/3
Hvμ = 740 Pμ vμb of this compound is high in the infrared (IR) region and gradually de­
creases in the visible and ultraviolet (UV) region as evident from the
where, Pμ is the Mulliken overlap population of the μ-type bond, and vμb Fig. 4(c and d). The static refractive index is found to be large for po­
is the bond volume of μ-type bond. larization along [100]. The nature of variation of the refractive index
The calculated values of Vickers hardness for Mg2Ir3Si and Li2IrSi3 and extinction coefficient roughly follows the fashion of the imaginary
are found to be 2.85 and 6.81 GPa, respectively (see Table 5). This and real part of the complex dielectric function, respectively.
hardness increase significantly when Li ion is substituted by Mg ion, and The absorption coefficient (α) indicates about the optimum solar
Ir and Si atoms exchange their positions in the structure of Li2IrSi3. energy conversion efficiency and how far light (specific energy) pene­
trate into the material before being absorbed. It is obvious that the
shapes of the absorption spectra are similar in the high energy region.
3.5. Optical properties The absorption start at 0 eV indicates the metallic nature of the com­
pounds of interest. There are several peaks are observed in Fig. 4(e).
The calculated optical properties such as dielectric function, refrac­ These peaks are due to the transition from Si p states to Ir d states. The
tive index, absorption spectrum, energy loss function, reflectivity and maximum absorption occurs between 12 and 25 eV. A strong absorption
optical conductivity of Mg2Ir3Si and Li2IrSi3 for photon energy up to 30 is observed in the UV region; however, it is weak in the IR region,
eV along the polarizing vectors [100] are illustrated in Fig. 4(a–h). For indicate that these compounds are promising as absorbing materials in
metallic compounds the inter-band and intra-band contributions to the UV region.
dielectric functions are considered here. We have used 0.5 eV as The spectra due to energy loss function (L) are presented in Fig. 4(f).
Gaussian smearing and 0.05 eV as damping for all calculations. The knowledge of energy loss function is very important in the dielectric
The dielectric function shows how a material interacts with the formalism, which is used to understand the screened excitation spectra.
incident electromagnetic waves which is closely related to the electronic The highest peak of the energy loss spectra appears in a particular
band structure. Due to having metallic nature of Mg2Ir3Si and Li2IrSi3, a incident light (energy), which gives the information about the bulk
Drude term is considered with unscreened plasma frequency of 10 eV. plasma frequency (ωp) that appears at ϵ2< 0 and ϵ1 = 0. The highest peak
The real and imaginary parts of dielectric function are shown in Fig. 4(a is observed at 15 and 25 eV for Li2IrSi3 and Mg2Ir3Si when light polarizes
and b). There is small peak in both the real and imaginary part. This peak along [100].
is related to the transition between valance band maxima (VBM) and The reflectivity (R) is defined as the ratio of the energy of a wave
conduction band minima (CBM). In the higher (~25 eV) energy range, reflected from a surface to the energy possessed by the wave striking the
the real part of dielectric function becomes unity and imaginary part of surface. Fig. 4(g) represents the reflectivity along [100] direction. It is
dielectric function tends to be zero. It indicates that in this region the observed that the reflectivity decrease sharply up to 5 eV and again
compounds become almost transparent with small absorption. From

Table 5
Calculated Mulliken bond number nμ, bond length dμ, bond overlap population Pμ, bond volume vb and bond hardness Hv of μ-type bond and Vickers hardness Hv of
μ μ

Mg2Ir3Si silicide along with Li2IrSi3.

Compounds Methods Bond nμ dμ (Å) Pμ vμb (Å3) Hμv (GPa) Hv (GPa)

Mg2Ir3Si GGA Si–Ir 12 2.44880 0.38 15.718 2.85 2.85

Li2IrSi3 GGA Si - Ir 12 2.46525 0.33 9.616 5.57 6.81
Si - Si 06 2.43154 0.56 9.227 10.20

5
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

Fig. 4. Optical parameters as a function of photon energy: (a) Real ε1, (b) Imaginary ε2 part of dielectric constant, (c) Refractive index n, (d) Extinction coefficient k,
(e) Absorption coefficient α, (f) Loss function L, (g) Reflectivity R and (h) Conductivity σ for Mg2Ir3Si and Li2IrSi3 silicide along [100] direction.

starts to increase at around 20 eV and reach the maximum value at Li et al. [22], a compound will be capable of reducing solar heating if it
around 25~27 eV. Although the reflectance varies in the energy range has reflectivity ~44% in the visible light region. Therefore, Mg2Ir3Si and
5–25 eV the shape of the spectra are almost similar. It is noteworthy that Li2IrSi3 might be promising candidate for the practical usage as a coating
reflectivity is always above 44% for Mg2Ir3Si and Li2IrSi3. According to material to avoid solar heating.

6
U. Jasia et al. Solid State Communications 334–335 (2021) 114361

The real part of optical conductivity (σ) is represented in Fig. 4(h). References
The optical conductivity starts at zero photon energy, indicating the
metallic nature of the titled compounds. The optical conductivity is [1] D. Hirai, R. Kawakami, O.V. Magdysyuk, R.E. Dinnebier, A. Yaresko, H. Takagi,
Superconductivity at 3.7 K in ternary silicide Li2IrSi3, J. Phys. Soc. Jpn. 83 (2014)
expected to be a good gauge of the photo-conductivity [23]. From Fig. 4 103703.
(h), it is also observed that both the silicides Mg2Ir3Si and Li2IrSi3 exhibit [2] K. Kudo, H. Hiiragi, T. Honda, K. Fujimura, H. Idei, M. Nohara, Superconductivity
high optical conductivity within the energy range of 0.75~4.0 eV along in Mg2Ir3Si: A fully ordered laves phase, J. Phys. Soc. Jpn. 89 (2020), 013701.
[3] S. Pyon, K. Kudo, J.I. Matsumura, H. Ishii, G. Matsuo, M. Nohara, H. Hojo, K. Oka,
[100] direction. M. Azuma, V.O. Garlea, K. Kodama, Superconductivity in noncentrosymmetric
iridium silicide Li2IrSi3, J. Phys. Soc. Jpn. 83 (2014), 093706.
4. Conclusions [4] M.A. Alam, M.A.K. Zilani, F. Parvin, M.A. Hadi, Physical properties of ternary
silicide superconductors Li2XSi3 (X = Rh, Os): An ab initio study, Int. J. Mod. Phys.
B 31 (2017) 1750135.
The structural, electronic, elasto-mechanical and optical properties [5] L.N. Cooper, Bound electron pairs in a degenerate Fermi gas, Phys. Rev. 104 (1956)
of new ternary silicide superconductor Mg2Ir3Si are investigated suc­ 1189.
[6] H. Witte, Untersuchungen im system Magnesium-mpfer-silicium mit besonderer
cessfully within the GGA. All the physical properties are also investi­
Beruecksichtigung des Schnittes MgCu2–MgSi2, Metallwirtsch. Metallwiss.
gated for isostructural silicide Li2IrSi3 for comparison. Both the Metalltech. 18 (1939) 459–463.
compounds studied are mechanically stable with satisfying Born sta­ [7] M.A. Hadi, M.A. Alam, M. Roknuzzaman, M.T. Nasir, A.K.M.A. Islam, S.H. Naqib,
bility criteria. The substitution of Li ion by Mg and the exchange of Structural, elastic, and electronic properties of recently discovered ternary silicide
superconductor Li2IrSi3: An ab-initio study, Chin. Phys. B 24 (2015) 117401.
atomic positions between Ir and Si in Mg2Ir3Si relative to Li2IrSi3 in­ [8] S.J. Clark, M.D. Segall, C.J. Pickard, P.J. Hasnip, M.I. Probert, K. Refson, M.
crease the lattice parameter a and reduce the lattice constant c, and C. Payne, First principles methods using CASTEP, Z. Kristallogr. Cryst. Mater. 220
consequently increase the cell volume V. The band structure as well as (2005) 567–570.
[9] D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue
DOS modifies significantly when Li ion is substituted by Mg ion, and Ir formalism, Phys. Rev. B 41 (1990) 7892.
and Si atoms exchange their positions in the structure of Li2IrSi3. The [10] T.H. Fischer, J. Almlof, General methods for geometry and wave function
metallic nature and ductility increase significantly when Li is substituted optimization, J. Phys. Chem. 96 (1992) 9768–9774.
[11] H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys.
by Mg, and Ir and Si atoms exchange their positions. Mg2Ir3Si is elasti­ Rev. B 13 (1976) 5188.
cally more anisotropic and easily machinable than Li2IrSi3. The Vickers [12] M. Born, On the stability of crystal lattices, Math. Proc. Camb. Philos. Soc. 36
hardness reduces significantly when Li ion is substituted by Mg ion, and (1940) 160–172.
[13] S.F. Pugh, XCII. Relations between the elastic moduli and the plastic properties of
Ir and Si atoms exchange their positions in Li2IrSi3. Both Mg2Ir3Si and polycrystalline pure metals, Philos. Mag. A 45 (1954) 823–843.
Li2IrSi3 silicides can be used as absorbent and coating material due to [14] I.N. Frantsevich, F.F. Voronov, S.A. Bokuta, Elastic Constants and Elastic Moduli of
their good absorption coefficient and reflectivity. Metals and Insulators Handbook, Naukova Dumka, Kiev, Ukraine, 1983.
[15] C. Zuo, B. Chen, C. Zhong, J. Zhao, The structural, electronic, elastic and
thermodynamic properties of V2AX (A = B, Al, Ga, In and TI; X = C and N): A DFT
Credit author statement calculation, Int. J. Mod. Phys. B 33 (2019) 1950359.
[16] L. Vitos, P. Korzhavyi, B. Johansson, Stainless steel optimization from quantum
U. Jasia: Investigation, Methodology; M.A. Alam: Software, Visu­ mechanical calculations, Nat. Mater. 2 (2003) 25–28.
[17] D.G. Pettifor, Theoretical predictions of structure and related properties of
alization, Data curation, Validation, Writing- Original draft, Supervi­ intermetallics, Mater. Sci. Technol. 8 (1992) 345–349.
sion; M.A.H. Shah: Visualization, Data curation, Writing-Reviewing and [18] X.D. He, Y. Bai, C. Zhu, Y. Sun, M. Li, M.W. Barsoum, General trends in the
Editing; M.A. Hadi: Conceptualization, Validation, Writing-Reviewing structural, electronic and elastic properties of the M3AlC2 phases (M= transition
metal): A first-principle study, Comput. Mater. Sci. 49 (2010) 691–698.
and Editing. [19] R.S. Mulliken, Electronic population analysis on LCAO-MO molecular wave
functions, J. Chem. Phys. 23 (1955) 1833–1840.
Declaration of competing interest [20] M.A. Alam, M.A. Hadi, M.T. Nasir, M. Roknuzzaman, F. Parvin, M.A.K. Zilani, A.K.
M.A. Islam, S.H. Naqib, Structural, elastic, and electronic properties of newly
discovered Li2PtSi3 superconductor: Effect of transition metals, J. Supercond. Nov.
The authors declare that they have no known competing financial Magn. 29 (2016) 2503–2508.
interests or personal relationships that could have appeared to influence [21] F. Gao, Theoretical model of intrinsic hardness, Phys. Rev. B 73 (2006) 132104.
[22] S. Li, R. Ahuja, M.W. Barsoum, P. Jena, B. Johansson, Optical properties of Ti3SiC2
the work reported in this paper. and Ti4AlN3, Appl. Phys. Lett. 92 (2008) 221907.
[23] G. Yu, C.H. Lee, A.J. Heeger, S.W. Cheong, Photoconductivity and optical
conductivity in lightly doped Nd2CuO4− δ, Physica C 203 (1992) 419–425.