Pressure study of monoclinic ReO2 up to 1.2 GPa using X-ray absorption spectroscopy and X-ray diffraction

Ferreira, F.F.; Corrêa, H.P.S.; Orlando, M.T.D.; Passamai, J.L.Jr; Orlando, C.G.P.; Cavalcante, I.P.; Garcia, F.; Tamura, E.; Martinez, L.G.; Rossi, J.L.; de Melo, F.C.L.

doi:10.1107/S0909049508036029

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Pressure study of monoclinic ReO₂ up to 1.2 GPa using X-ray absorption spectroscopy and X-ray diffraction

F. F. Ferreira, H. P. S. Corrêa, M. T. D. Orlando, J. L. Passamai Jr, C. G. P. Orlando, I. P. Cavalcante, F. Garcia, E. Tamura, L. G. Martinez, J. L. Rossi and F. C. L. de Melo

The crystal and local atomic structure of monoclinic ReO₂ (α-ReO₂) under hydrostatic pressure up to 1.2 GPa was investigated for the first time using both X-ray absorption spectroscopy and high-resolution synchrotron X-ray powder diffraction and a home-built B₄C anvil pressure cell developed for this purpose. Extended X-ray absorption fine-structure (EXAFS) data analysis at pressures from ambient up to 1.2 GPa indicates that there are two distinct Re—Re distances and a distorted ReO₆ octahedron in the α-ReO₂ structure. X-ray diffraction analysis at ambient pressure revealed an unambiguous solution for the crystal structure of the α-phase, demonstrating a modulation of the Re—Re distances. The relatively small portion of the diffraction pattern accessed in the pressure-dependent measurements does not allow for a detailed study of the crystal structure of α-ReO₂ under pressure. Nonetheless, a shift and reduction in the (011) Bragg peak intensity between 0.4 and 1.2 GPa is observed, with correlation to a decrease in Re—Re distance modulation, as confirmed by EXAFS analysis in the same pressure range. This behavior reveals that α-ReO₂ is a possible inner pressure gauge for future experiments up to 1.2 GPa.

Keywords: X-ray diffraction; pressure; EXAFS; ReO₂.

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Supporting information

Crystallographic Information File (CIF) https://doi.org/10.1107/S0909049508036029/wa5006sup1.cif
Contains datablocks REO2_publ, REO2_overall, REO2_phase_1, REO2_phase_2, REO2_phase_3, REO2_p_01

Computing details top

Figures top

(REO2_phase_1) top

Crystal data top

O₂Re	β = 120.2721 (18)°
M_r = 218.21	V = 129.17 (1) Å³
Monoclinic, P2₁/c	Z = 4
a = 5.61113 (15) Å	? radiation, λ = 1.239998 Å
b = 4.80456 (9) Å	?, ? × ? × ? mm
c = 5.54783 (17) Å

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

Least-squares matrix: full	8600 data points
R_p = 0.092	Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.858 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.4445 #13(S400 ) = 2.2E+00 #14(S040 ) = 6.8E+00 #15(S004 ) = 7.4E+00 #16(S220 ) = 3.5E-01 #17(S202 ) = 5.9E+00 #18(S022 ) = -3.1E+00 #19(S301 ) = 4.4E+00 #20(S103 ) = 5.9E+00 #21(S121 ) = -3.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 16 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.680 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.9810 #13(S400 ) = 4.1E-02 #14(S004 ) = 3.0E-05 #15(S220 ) = -2.6E-02 #16(S202 ) = 6.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 18 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 10.115 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.6973 #13(S400 ) = 7.4E-01 #14(S040 ) = 2.2E+00 #15(S004 ) = 3.8E+00 #16(S220 ) = 7.7E-01 #17(S202 ) = -6.7E-01 #18(S022 ) = 5.0E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.121	57 parameters
R_exp = 0.091	0 restraints
R(F²) = 0.05927	(Δ/σ)_max = 0.05
χ² = 1.769	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 43.6672 2: -14.9861 3: 2.15605 4: -1.46007 5: -0.693433 6: 2.03766 7: -3.19664 8: 3.10886 9: -0.434656 10: -1.86818 11: 4.98375 12: -3.92371 13: 1.06103 14: -0.269726

Crystal data top

O₂Re	β = 120.2721 (18)°
M_r = 218.21	V = 129.17 (1) Å³
Monoclinic, P2₁/c	Z = 4
a = 5.61113 (15) Å	? radiation, λ = 1.239998 Å
b = 4.80456 (9) Å	?, ? × ? × ? mm
c = 5.54783 (17) Å

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

R_p = 0.092	χ² = 1.769
R_wp = 0.121	8600 data points
R_exp = 0.091	57 parameters
R(F²) = 0.05927	0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Re1	0.2379 (2)	−0.0026 (15)	0.0067 (3)	0.01831 (11)*
O1	0.112 (5)	0.200 (5)	0.227 (4)	0.01831 (11)*
O2	0.387 (5)	0.709 (5)	0.293 (4)	0.01831 (11)*

(REO2_phase_2) top

Crystal data top

O₃Re	V = 105.29 (1) Å³
M_r = 234.20	Z = 2
Tetragonal, P4/mbm	? radiation, λ = 1.239998 Å
a = 5.30107 (11) Å	?, ? × ? × ? mm
c = 3.74690 (16) Å

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

Least-squares matrix: full	8600 data points
R_p = 0.092	Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.858 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.4445 #13(S400 ) = 2.2E+00 #14(S040 ) = 6.8E+00 #15(S004 ) = 7.4E+00 #16(S220 ) = 3.5E-01 #17(S202 ) = 5.9E+00 #18(S022 ) = -3.1E+00 #19(S301 ) = 4.4E+00 #20(S103 ) = 5.9E+00 #21(S121 ) = -3.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 16 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.680 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.9810 #13(S400 ) = 4.1E-02 #14(S004 ) = 3.0E-05 #15(S220 ) = -2.6E-02 #16(S202 ) = 6.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 18 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 10.115 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.6973 #13(S400 ) = 7.4E-01 #14(S040 ) = 2.2E+00 #15(S004 ) = 3.8E+00 #16(S220 ) = 7.7E-01 #17(S202 ) = -6.7E-01 #18(S022 ) = 5.0E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.121	57 parameters
R_exp = 0.091	0 restraints
R(F²) = 0.05927	(Δ/σ)_max = 0.05
χ² = 1.769	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 43.6672 2: -14.9861 3: 2.15605 4: -1.46007 5: -0.693433 6: 2.03766 7: -3.19664 8: 3.10886 9: -0.434656 10: -1.86818 11: 4.98375 12: -3.92371 13: 1.06103 14: -0.269726

Crystal data top

O₃Re	V = 105.29 (1) Å³
M_r = 234.20	Z = 2
Tetragonal, P4/mbm	? radiation, λ = 1.239998 Å
a = 5.30107 (11) Å	?, ? × ? × ? mm
c = 3.74690 (16) Å

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

R_p = 0.092	χ² = 1.769
R_wp = 0.121	8600 data points
R_exp = 0.091	57 parameters
R(F²) = 0.05927	0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Re1	0.0	0.0	0.5	0.0175 (11)*
O1	0.0	0.0	0.0	0.0175 (11)*
O2	0.102 (9)	0.602 (9)	0.5	0.0175 (11)*

(REO2_phase_3) top

Crystal data top

O₂Re	c = 4.6129 (2) Å
M_r = 218.21	V = 124.83 (1) Å³
Orthorhombic, Pbcn	Z = 4
a = 4.8040 (2) Å	? radiation, λ = 1.239998 Å
b = 5.6332 (4) Å	?, ? × ? × ? mm

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

Least-squares matrix: full	8600 data points
R_p = 0.092	Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.858 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.4445 #13(S400 ) = 2.2E+00 #14(S040 ) = 6.8E+00 #15(S004 ) = 7.4E+00 #16(S220 ) = 3.5E-01 #17(S202 ) = 5.9E+00 #18(S022 ) = -3.1E+00 #19(S301 ) = 4.4E+00 #20(S103 ) = 5.9E+00 #21(S121 ) = -3.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 16 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 2.680 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.9810 #13(S400 ) = 4.1E-02 #14(S004 ) = 3.0E-05 #15(S220 ) = -2.6E-02 #16(S202 ) = 6.3E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0, CW Profile function number 4 with 18 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 0.000 #4(GP) = 0.000 #5(LX) = 10.115 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.3326 #9(sfec) = 0.00 #10(S/L) = 0.0063 #11(H/L) = 0.0063 #12(eta) = 0.6973 #13(S400 ) = 7.4E-01 #14(S040 ) = 2.2E+00 #15(S004 ) = 3.8E+00 #16(S220 ) = 7.7E-01 #17(S202 ) = -6.7E-01 #18(S022 ) = 5.0E-01 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
R_wp = 0.121	57 parameters
R_exp = 0.091	0 restraints
R(F²) = 0.05927	(Δ/σ)_max = 0.05
χ² = 1.769	Background function: GSAS Background function number 1 with 14 terms. Shifted Chebyshev function of 1st kind 1: 43.6672 2: -14.9861 3: 2.15605 4: -1.46007 5: -0.693433 6: 2.03766 7: -3.19664 8: 3.10886 9: -0.434656 10: -1.86818 11: 4.98375 12: -3.92371 13: 1.06103 14: -0.269726

Crystal data top

O₂Re	c = 4.6129 (2) Å
M_r = 218.21	V = 124.83 (1) Å³
Orthorhombic, Pbcn	Z = 4
a = 4.8040 (2) Å	? radiation, λ = 1.239998 Å
b = 5.6332 (4) Å	?, ? × ? × ? mm

Data collection top

2θ_min = 13.998°, 2θ_max = 99.988°, 2θ_step = 0.01°

Refinement top

R_p = 0.092	χ² = 1.769
R_wp = 0.121	8600 data points
R_exp = 0.091	57 parameters
R(F²) = 0.05927	0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Re1	0.0	0.1089 (4)	0.25	0.0072 (3)*
O1	0.239 (4)	0.359 (8)	0.109 (4)	0.0072 (3)*

Experimental details

	(REO2_phase_1)	(REO2_phase_2)	(REO2_phase_3)
Crystal data
Chemical formula	O₂Re	O₃Re	O₂Re
M_r	218.21	234.20	218.21
Crystal system, space group	Monoclinic, P2₁/c	Tetragonal, P4/mbm	Orthorhombic, Pbcn
Temperature (K)	?	?	?
a, b, c (Å)	5.61113 (15), 4.80456 (9), 5.54783 (17)	5.30107 (11), 5.30107, 3.74690 (16)	4.8040 (2), 5.6332 (4), 4.6129 (2)
α, β, γ (°)	90, 120.2721 (18), 90	90, 90, 90	90, 90, 90
V (Å³)	129.17 (1)	105.29 (1)	124.83 (1)
Z	4	2	4
Radiation type	?, λ = 1.239998 Å	?, λ = 1.239998 Å	?, λ = 1.239998 Å
Specimen shape, size (mm)	?, ? × ? × ?	?, ? × ? × ?	?, ? × ? × ?

Data collection
Diffractometer	?	?	?
Specimen mounting	?	?	?
Data collection mode	?	?	?
Scan method	?	?	?
2θ values (°)	2θ_min = 13.998 2θ_max = 99.988 2θ_step = 0.01	2θ_min = 13.998 2θ_max = 99.988 2θ_step = 0.01	2θ_min = 13.998 2θ_max = 99.988 2θ_step = 0.01

Refinement
R factors and goodness of fit	R_p = 0.092, R_wp = 0.121, R_exp = 0.091, R(F²) = 0.05927, χ² = 1.769	R_p = 0.092, R_wp = 0.121, R_exp = 0.091, R(F²) = 0.05927, χ² = 1.769	R_p = 0.092, R_wp = 0.121, R_exp = 0.091, R(F²) = 0.05927, χ² = 1.769
No. of data points	8600	8600	8600
No. of parameters	57	57	57

Computer programs: GSAS.

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