Crystal structure and bonding in the new mineral AsSbO 3 . Marcus J. Origlieri 1 *, Robert T. Downs 1§ , Michael D. Carducci 1 Kevin M. Rosso 2 , G. V. Gibbs 3 1 Department of Geosciences, University of Arizona Tucson, Arizona 85719-0077 USA 2 Pacific Northwest National Laboratory P.O. Box 999, K8-96, Richland, WA 99352 USA 3 Department of Geological Sciences, Virginia Polytechnic Institute Blacksburg, VA 24061-0420 USA *[email protected]; §[email protected]
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Crystal structure and bonding in the new mineral AsSbO 3. Marcus J. Origlieri 1 *, Robert T. Downs 1§, Michael D. Carducci 1 Kevin M. Rosso 2, G. V. Gibbs.
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Crystal structure and bonding in the new mineral AsSbO3.
Marcus J. Origlieri1*, Robert T. Downs1§, Michael D. Carducci1
Kevin M. Rosso2, G. V. Gibbs3
1Department of Geosciences, University of Arizona Tucson, Arizona 85719-0077 USA2Pacific Northwest National Laboratory P.O. Box 999, K8-96, Richland, WA 99352 USA3Department of Geological Sciences, Virginia Polytechnic Institute Blacksburg, VA 24061-0420 USA*[email protected]; §[email protected]
unknown mineral
• EDS indicated only major As, Sb
Raman spectrum
100 200 300 400 500 600 700 800 900
Raman shift (rel. cm- 1)
Inte
ns
ity
(arb
itra
ry u
nits
)
new mineral
leiteite
crystal morphology
Palache (1934)
microprobe chemical analysis
Average of 10 standardized WDS analyses:
Sb2O3 55.77%
As2O3 45.15% total 101.92%
EMPIRICAL FORMULA = As1.088Sb0.912O3
standards enargite Cu3AsS4
stibiotantalite SbTaO4
X-ray diffraction
• streaky data
• merged well for space group P21/n (Rsym = 2.71%)
crystal structure solution
• Matches synthetic AsSbO3 (Bodenstein et al. 1983)
• Trigonal pyramids of AsO3 and SbO3 link corners to form infinite sheets of composition AsSbO3 stacked along b
crystal structure solution
new mineral vs. claudetite
new mineral claudetite
chemistry AsSbO3 As2O3
space group P21/n P21/n
a 4.5757(4) Å 4.5460(4) Å
b 13.1288(13) Å 13.0012(14) Å
c 5.4216(5) Å 5.3420(5) Å
b 95.039(4)° 94.329(2)°
V 324.44(5) Å3 314.83(5) Å3
Z 4 4
dcalc 5.009 g/cm3 4.174 g/cm3
bond distancesnew mineralAs−O1 1.773(7) Å Sb−O11.978(7) ÅAs−O2 1.781(6) Å Sb−O22.006(6) ÅAs−O3 1.792(6) Å Sb−O31.995(7) Å<R(As−O)> 1.782 Å <R(Sb−O)> 1.993 Å
claudetiteAs1−O1 1.772(5) Å As2−O1 1.783(5) ÅAs1−O2 1.788(4) Å As2−O2 1.805(5) ÅAs1−O3 1.790(5) Å As2−O3 1.790(5) Å<R(As1−O)> 1.783 Å <R(As2−O)> 1.793 Å
Sb in AsSbO3 structure preferentially occupies the As2 site of claudetite
<R(As2−O) ~ <R(As1−O)>
<O−As2−O> < <O−As1−O>
94.8° < 98.1°
Sb prefers a smaller O−M−O for MO3 than As
ordering of As and Sb
synthetic naturalBodenstein et al. (1983) this study
<R(As−O)>1.80 Å 1.782 Å <R(Sb−O)> 1.95 Å 1.993 Å
The more extreme <R(As−O)> and <R(Sb−O)> indicate a higher degree of ordering in natural AsSbO3 than synthetic material
formula of new mineral
• Natural AsSbO3 shows a higher degree of As/Sb ordering than synthetic material
• Crystal structure refinement gives lower residual value (5.66%) with idealized chemistry than with microprobe chemistry
ACTUAL CHEMISTRY = AsSbO3
bonding in arsenites
• Between sheets of the leiteite (ZnAs2O4) structure, Ghose (1987) argues “long As-O interactions must be considered as weak bonds, which hold the composite layers together.”
• Pertlik (1975) notes that As-O distances of 3.15 Å in trippkeite result from steric effects.
definition of bonding
• Bader (1990) defines a bonded interaction exists when electron density shows both:– BOND PATH – a continuous path of local
maxima of electron density in the perpendicular plane between two maxima of electron density (i.e. atoms)
– BOND CRITICAL POINT – a (3,−1) saddle point of electron density along the bond path located between the atoms
electron density distribution
Sb−O12.947 Å (intra-
layer)
Sb−O23.237 Å(inter-
layer)
quantum calculations
• Follow Density Function Theory
• Linear combinations of numerically solved wave functions
• Basis sets optimized for Crystal98 (Pisani et al. 2000)
• Uses coordinates of atoms and unit cell from crystal structure refinement
• Search radius 9 Å
bonding topology
• three groups of bonds distinguished their electron densities at the bond critical points
– close contacts (rc) = 0.984−1.012 As−O
(rc) = 0.730−0.757 Sb−O
– intra-layer bonds (rc) = 0.169−0.134
– inter-layer bonds (rc) = 0.084−0.062
intra-layer bonds
responsible for the corrugation of the sheet
Three separate bonds:
Sb−O3 2.791 Å
As−O2 2.903 Å
Sb−O1 2.947 Å
inter-layer bonds
Two weakest bonds in the structure are between sheets:
Sb−O2 3.237 Å
As−O3 3.346 Å
Responsible for perfect (010) cleavage of the mineral
related structures
• Cubic As2O3 (arsenolite) and Sb2O3 (senarmontite) have structures consisting of M4O6 molecular units.
• Oxygen atoms form corners of octahedra with metal atoms centered above alternating faces of the octahedron
• Cubic AsSbO3 is a solid solution between As2O3 and Sb2O3
crystal structure of cubic As2O3
view down [110]view down [010]
cubic As2O3 and Sb2O3
• As2O3 (Ballirano & Maras, 2002)
– a = 11.074 Å– R(As−O) = 1.786(2) Å O−As−O = 98.4(2)°
• Sb2O3 (Whitten et al. 2004)
– a = 11.116 Å– R(Sb−O) = 1.978(1) Å O−Sb−O = 95.9(1)°