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 COMMAT 5582 No. of Pages 1, Model 5G
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Graphical abstract

Pressure induced metallization of fordite SnNb2O6 from first principles pp xxx–xxx

S.F. Matar *, M.A. Subramanian, J. Etourneau

Highlights

 Equations of states of foordite SnNb2O6 in columbite and trirutile suggest them as HP forms.  HP forms are harder and found at higher
energy/smaller volumes.  Drastic electronic effects pertaining to the oxidation of Sn with metallization under pressure.

1
 COMMAT 5582 No. of Pages 6, Model 5G
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Computational Materials Science xxx (2013) xxx–xxx

1

Contents lists available at ScienceDirect

Computational Materials Science

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

4
5

3 Pressure induced metallization of fordite SnNb2O6 from first principles

6 Q1 S.F. Matar a,b,⇑, M.A. Subramanian c, J. Etourneau a,b
7 a
CNRS, ICMCB, UPR 9048, F-33600 Pessac, France
8 b
Univ. Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France
9 c
Oregon State University, Department of Chemistry, Corvallis, OR 97331-4003, USA

11
10
12
a r t i c l e i n f o a b s t r a c t
1
2 4
7
15 Article history: From DFT based calculations establishing energy-volume equations of state, a proposition of high 28
16 Received 26 September 2013 pressure candidate structures with reduced volumes, namely columbite and trirutile are proposed for for- 29
17 Received in revised form 13 December 2013 dite mineral SnNb2O6. The key effect is the destabilization of divalent tin in fordite towards tetravalent 30
18 Accepted 14 December 2013
state upon compression. This is helped with smaller size tetravalent tin. The remarkable electronic struc- 31
19 Available online xxxx
ture change is the transformation from semi-conducting fordite to metallic high pressure forms thanks to 32
the electron transfer from Sn to Nb and O as quantified from charge density analyses. 33
20 Keywords:
Ó 2013 Published by Elsevier B.V. 34
21 Fordite mineral
22 DFT
23 High pressure
24 Equation of states
25 Density of states
26
35
36
37 1. Introduction groups are corner sharing and run as Nb4O12 files along a direction, 60
i.e. parallel to (b, c) plane; they are separated by Sn (Fig. 1a). 61
38 The divalent state of Sn is not common in oxides. In spite of the In AB2O6 stoichiometry several divalent alkaline earth ANb2O6 62
39 existence of SnO, it is mostly tetravalent tin, SnIV which is encoun- such as A = Ca [4] crystallize in the columbite-type structure with 63
40 tered as in cassiterite mineral: SnO2. Also divalent tin is less stabi- orthorhombic space group (SG) Pbcn and four FU per unit cell. The 64
41 lized than in Pb compounds. In the context of the search for lead structure shown in Fig. 1b is close to that of SnNb2O6 for the stack- 65
42 and bismuth free compounds for applications in actuators, respect- ing of the octahedra. On the other side FeTa2O6 crystallizes in 66
43 ful of the environment, we recently investigated the stability and tetragonal trirutile (P42/mnm SG) with two FU per unit cell [5]. In 67
44 ferroelectric properties of perovskite derived SnTiO3 from first spite of the large number of compounds crystallizing in the colum- 68
45 principles [1]. Indeed the large size of SnII could enable its location bite structure, the Sn member does not belong to them. Size consid- 69
46 at the A corner sites in ABO3 perovskite. However its synthesis has erations pertaining to the large ionic radius of Sn seem to play an 70
47 not been successful as yet. important effect. This provides an exemplary case study of evaluat- 71
48 SnII is found in the mineral fordite (SnNb1.5Ta0.5O6) [2] and the ing the pressure effects on the structure both from the crystallogra- 72
49 synthesis of SnNb2O6 ternary oxide requires a reducing atmo- phy point of view as well as from the electronic structure one. This 73
50 sphere to be obtained pure. It crystallizes in the monoclinic crystal pertains to search for potential high pressure (HP) phases on one 74
51 system with C2/c space group SG and four formula units FU per hand and to investigate the changes in the electronic states of the 75
52 unit cell. Sn is five-fold coordinated with oxygen with an average p (Sn) and d (Nb) elements in such conditions on the other hand. 76
53 d(Sn–O)  2.3 Å, which can be expected from the divalent state In this paper we investigate the columbite and trirutile struc- 77
54 of tin: r(SnII) = 1.12 Å, versus r(SnIV) = 0.70 Å. Actually the earliest tures as potential candidates for HP SnNb2O6, based on computa- 78
55 structural studies erroneously proposed tin to be tetravalent in a tions within the density functional theory DFT [6]. Note that 79
56 modified stoichiometry SnIVTa2O7 [3]. In fordite, niobium atoms cation defect perovskite model was considered based on CexNb2O6 80
57 are found in two non equivalent sites in a distorted octahedral [7] in the preliminary investigations but the geometry optimized 81
58 coordination with oxygen. The average Nb–O length is 2 Å. volume was found much larger (504 Å3/cell) than fordite SnNb2O6 82
59 NbO6 octahedra are edge sharing and form Nb2O10 groups. These (cf. Table 1). From geometry optimizations and energy quantities 83
the energy-volume equations of states EOS are derived for the 84
three structures leading to propose columbite and trirutile as HP 85
Q2 ⇑ Corresponding author at: CNRS, ICMCB, UPR 9048, F-33600 Pessac, France. forms. Analysis of the electronic structure shows drastic electronic 86
Tel.: +33 540002690; fax: +33 54002761.
effects pertaining to the oxidation of Sn and subsequent 87
E-mail addresses: abouliess@gmail.com, matar@icmcb-bordeaux.cnrs.fr
(S.F. Matar).
metallization. 88

0927-0256/$ - see front matter Ó 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.commatsci.2013.12.027

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2 S.F. Matar et al. / Computational Materials Science xxx (2013) xxx–xxx

Fig. 1. SnNb2O6 structures. Room pressure fordite (a), proposed high pressure columbite (b) and trirutile (c). Green, grey and red spheres represent Sn, Nb and O respectively.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Table 1
SnNb2O6: Experimental and (calculated) lattice parameters.

Foorderite C2/c #15

Sn (4a) 000 Nb, O1, O2, O3 (8f) x,y,z [2]
a = 17.093 (17.07) Å
b = 4.877 (4.92) Å
c = 5.558 (5.40) Å
b = 90.85° (90.67°)
V/4 FU = 463.3 Å3 (454 Å3)

Atom x y z
Sn 0 0.240 (0.24) 1=
4
Nb 0.330 (0.32) 0.258 (0.26) 0.328 (0.33)
O1 0.427 (0.43) 0.420 (0.43) 0.401 (0.41)
O2 0.357 (0.37) 0.042 (0.04) 0.069 (0.07)
O3 0.219 (0.22) 0.063 (0.06) 0.353 (0.35)

Columbite Pbcn #60

Sn (4c) 0y1=4 ; Nb, O1, O2, O3 (8d) x,y,z. Exp. data from CoNb2O6 [4]
a = 14.125 (14.55) Å
b = 5.701 (5.77) Å
c = 5.038 (5.20) Å
V/4 FU = 405.69 Å3 (436.56 Å3)

Atom x y Z
Co (Sn) 0 0.158 (0.160) 1=
4
Nb 0.161 (0.167) 0.361 (0.355) 0.780 (0.769)
O1 0.094 (0.090) 0.372 (0.387) 0.447 (0.434)
O2 0.082 (0.079) 0.117 (0.122) 0.897 (0.912)
O3 0.238 (0.243) 0.151 (0.141) 0.594 (0.604)

Trirutile P42/mnm #136

Fe (Sn) (2a) 000; Ta (Nb) (4e) 00z, O1 (4f) x,x,0; O2 (8j) x,x,z. Exp. data from FeTa2O6 [5]
a = 4.794 (4.87) Å
c = 9.192 (9.17) Å
V = 211.25 Å3 (217.65 Å3)
V/4 FU = 422.50 Å3 (435.30 Å3)

Atom x y Z
Fe (Sn) 0 0 0
Ta (Nb) 0 0 0.333 (0.347)
O1 0.307 (0.288) 0.307 (0.288) 0
O2 0.297 (0.293) 0.297 (0.293) 0.322 (0.328)

89 2. Computational details cohesive energy calculations. For this we use the projector aug- 92
mented wave (PAW) method [8,9], with the generalized gradient 93
90 Within DFT, the Vienna ab initio simulation package (VASP) approximation (GGA) scheme following Perdew, Burke and Ernzer- 94
91 based on plane waves [8] allows geometry optimization and hof (PBE) [10]. Preliminary calculations with local density approx- 95

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S.F. Matar et al. / Computational Materials Science xxx (2013) xxx–xxx 3

96 imation LDA [11] led to largely underestimated volumes versus the SnNb2O6
97 experiment. The conjugate-gradient algorithm [12] is used in this C2/c : E 0 = -149.85 eV; B 0 = 190 GPa; V 0 = 241.76 Å
3

98 computational scheme to relax the atoms. The tetrahedron method P42 /mnm: E0 = -148.10 eV; B 0 = 218 GPa; V 0 = 218.90 Å
3

-70 3
99 with Blöchl corrections [9] as well as a Methfessel–Paxton [13] Pbcn : E0 = -147.23 eV; B 0 = 217 GPa; V0 = 218.28 Å
100 scheme are applied for both geometry relaxation and total energy -80

101 calculations. Brillouin-zone (BZ) integrals are approximated using -90

the special k-point sampling. The optimization of the structural

Energy (eV)
102 -100
103 parameters is performed until the forces on the atoms are less than
-110
104 0.02 eV/Å and all stress components below 0.003 eV/Å3. The calcu-
-120
105 lations are converged at an energy cut-off of 500 eV for the plane-
106 wave basis set with respect to the k-point integration up to 8  8 -130
107  13 (kx, ky, kz) for best convergence and relaxation to zero strains. -140
108 The calculations are scalar relativistic and assume spin degenerate -150 Ptransition ~23 GPa
109 total spins.
100 120 140 160 180 200 220 240 260 280 300 320 340
110 The all electrons scalar-relativistic augmented spherical wave 3
111 (ASW) method [14,15] is subsequently used for a full description Volume (Å ) / 2 FU
112 of the electronic structure and the properties of chemical bonding
Fig. 2. SnNb2O6 E(V) curves for room pressure foordite and high pressure columbite
113 based on the analysis of the overlap integrals Sij with the crystal and trirutile. Fit values from Birch EOS are given in the insert.
114 orbital overlap populations COOP following Hoffmann [16]. In the
115 plots, positive, negative, and zero COOP indicate bonding, anti-
116 bonding, and non-bonding interactions, respectively. required for the transformation: P  23 GPa. This can be achieved 157
using a diamond anvil cell device [19]. 158

117 3. Results and discussion 3.2. Electronic configurations and electronic structures 159

118 3.1. Geometry optimizations and equations of state We further assess these results by analyzing the charge density 160
issued from the self consistent calculations using the AIM (atoms 161
119 The initial and optimized crystal structure results are given in in molecules theory) approach [20] developed by Bader who 162

120 Table 1. Starting atomic positions for Foordite SnTa2O6, are those devised an intuitive way of splitting molecules into atoms as based 163
121 of the initial paper [2] whereas for the candidate HP phases we purely on the electronic charge density. Typically in chemical 164

122 started from CoNb2O6 [4] and FeTa2O6 [5] structural data. The systems, the charge density reaches a minimum between atoms 165
123 calculated volume of fordite is slightly smaller than experimental and this is a natural region to separate them from each other. Such 166

124 value. Relatively good agreement with the experimental data can an analysis can be useful when trends between similar compounds 167
125 be traced out for the atomic positions. In both columbite and trir- are examined; they do not constitute a tool for evaluating absolute 168

126 utile structures the volumes show close magnitudes, systemati- ionizations. The results of computed charges (Q) are such that they 169
127 cally smaller than fordite volume. This trend lets suggest that the lead to neutrality when the respective multiplicities are accounted 170

128 two hypothesized forms can be considered as candidates for high for; the obtained values for SnNb2O6 in the three forms are: 171
129 pressure transformation of fordite. Also it is interesting to note a
130 decrease of the Sn–O shortest distance from 2.2 down to 1.9 Å. This Fordite: Q(Sn) = +2.47; Q(Nb) = +3.31; Q(O1) = 1.72; Q(O2) 172
131 should involve enhanced Sn–O bonding as argued upon in the next = 1.41; Q(O3)=1.42. 173

132 section. It will be shown that this is connected with a change in the Columbite: Q(Sn) = +4.00; Q(Nb) = +2.99; Q(O1) = 1.71; Q(O2) 174
133 electronic configurations. = 1.82; Q(O3) = 1.46. 175

134 The structural modifications can be better assessed from plot- Trirutile: Q(Sn) = +4.00; Q(Nb) = +2.89; Q(O1) = 1.65; Q(O2) 176
135 ting the energy (E) volume (V), E = f(V) calculated around the opti- = 1.62. 177

136 mized parameters in Table 1 for the three phases and establish the 178
137 corresponding equations of states (EOS). The curves are gathered in Although the charge on Sn is 2+ in fordite, it is calculated close 179

138 Fig. 2. Besides the above finding of smaller volume columbite and to divalent (SnII) and contrasts well with the large change of oxida- 180
139 trirutile SnNb2O6, confirmed here, the ambient pressure curve of tion state of Sn to tetravalent (SnIV) in the two HP forms. The 181

140 foordite is found at lower energy than the other two curves (col- charge transfer is then towards niobium as well as oxygen. 182
141 umbite and trirutile) which are very close together. The fits by Schematically with pressure, Sn changes from divalent to tetrava- 183

142 Birch EOS [17] up to the third order: lent and the electrons (formally) transferred to Nb reduce it from 184
pentavalent (NbV) to tetravalent (NbIV). This observation is only 185
143
9 2 9 3
found in the Sn compound, i.e. in FeTa2O6 and in CoNb2O6 per se, 186
EðVÞ ¼ E0 ðV 0 Þ þ V 0 B0 ½ðV 0 =VÞ2=3  1 þ B0 ðB0  4ÞV 0 ½ðV 0 =VÞ2=3  1 the calculations confirm the divalent character of Fe/Co and the 187
145 8 16
pentavalent character of Nb. The slightly larger reduction of Nb 188
146 provide equilibrium parameters E0, V0, B0 and B0 respectively for the in trirutile candidate HP structure could be at the origin of its lar- 189
147 energy, the volume, the bulk modulus and its pressure derivative. ger stabilization versus columbite. 190
148 The obtained values with a goodness of fit v2  106 are displayed The above observations should be of significant consequence on 191
149 in the insert of Fig. 2. They confirm the trends inferred from the the changes of the electronic structures which are discussed from 192
150 visual inspection showing that the columbite and trirutile struc- the electronic density of states DOS obtained with the ASW meth- 193
151 tures are close, with the latter at lower energy (<1 eV). Then the od using the optimized structure parameters (Table 1). The site 194
152 two forms can be considered as HP candidates for fordite. In all projected DOS in the three forms are shown in Fig. 3. Low energy 195
153 phases the pressure derivative of the bulk modulus B0, B0 is 4, a va- lying filled Sn d states are not shown. Visual inspection shows a 196
154 lue usually encountered in oxides [18]. difference between Fig. 3a exhibiting fordite as semi-conducting 197
155 The smaller volumes lead to 30 GPa larger bulk moduli. The at room pressure with 1.8 eV gap, contrary to the two proposed 198
156 magnitudes can be used to provide an estimation of the pressure HP forms which are conducting thanks to the crossing of the lower 199

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4 S.F. Matar et al. / Computational Materials Science xxx (2013) xxx–xxx

200 part of Nb d states by the Fermi level EF (Fig. 3b and c). Note that Nb
201 being an early element of the 2nd transition metal period, its little
202 filled d states are centered above the top of the valence band (EV) in
203 Fig. 3a and EF in Fig. 3b and c. Low energy lying Sn s states are
204 found at the bottom part of the valence band with decreasing ener-
205 gies from 7 eV (Fig. 3a) to 9 eV (Fig. 3b) and 10 eV (Fig. 3c).
206 The itinerant part of Nb states, oxygen and tin p states are found
207 in 5 eV broad band with the VB where the quantum mixing
208 occurs leading to the chemical bonding. The 1.8 eV band gap in
209 Fig. 3a is found at lower energy in the other two subfigures. Then
210 major changes are in a quasi rigid shift of the DOS to lower ener-
211 gies due to the larger filling of Nb d states upon reducing with extra
212 electrons transferred from Sn, leading to the metallization mainly
213 caused by electrons from Nb d states.
214 Lastly we comment on the modification of the metal-oxygen
215 bonding strengths upon going from the room pressure SnNb2O6

Fig. 4. Comparative metal-oxygen chemical bonding in (a) room pressure SnNb2O6

and (b) high pressure trirutile.

to the trirutile high pressure candidate. Preliminary plots for 216

metal-metal bonding strength showed very small magnitudes as 217
with respect to metal-oxygen. Fig. 4 shows for SnNb2O6 the com- 218
parative metal-oxygen chemical bonding regrouping all oxygen 219
sites for the room pressure and the high pressure trirutile struc- 220
tures. The features of energy gap and metallization are observed 221
as in the relevant DOS panels. As a common result the Nb–O COOP 222
are larger than Sn–O due to the twice larger Nb equivalents in the 223
unit cell. Whereas the Sn–O COOP are smeared over the valence 224
band and present low intensity in room pressure fordite, large 225
changes are observed in the trirutile exhibiting high magnitude 226
Sn–O bonding COOPs in a narrow energy range from 8 to 227
7 eV. The metallization is concomitant with the onset of anti- 228
bonding NbO COOP at EF. In both panels the bonding COOP are 229
followed at higher energy by small antibonding contribution with 230
negative magnitudes within the valence band but the major anti- 231
bonding COOP, mainly for Nb–O, are found within the conduction 232
band. These qualitative results, especially for Sn–O enhanced 233
bonding behavior reflect the observed changes in the interatomic 234
distances with pressure. 235

4. Concluding remarks 236

From DFT based calculations establishing energy-volume equa- 237

tions of state, a proposition of high pressure candidate structures 238
for fordite has been provided. The key effect is in the destabiliza- 239
tion of divalent tin in fordite towards tetravalent state upon com- 240
pression. This is helped with smaller size tetravalent tin. The 241
remarkable electronic structure change is the transformation from 242
Fig. 3. SnNb2O6 site projected DOS: (a) room pressure fordite, (b) HP columbite and semi-conducting fordite to metallic high pressure forms thanks to 243
(c) HP trirutile. the electron transfer from Sn to Nb and O as quantified from charge 244

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S.F. Matar et al. / Computational Materials Science xxx (2013) xxx–xxx 5

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diamond_anvil.html. 284
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