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EXAFS investigation of the local structure in URu 2-x Fe x Si 2 : Evidence for distortions below 100 K

X-ray absorption measurements at the U L III , Ru K , and Fe K edges are reported for the hidden order (HO) material URu 2 - x Fe x Si 2 ( x = 0 , 0.05, 0.08, 0.10, 0.12, 0.15, and 0.20) as a function of x and temperature T . Furthermore, when Fe is substituted for Ru, the local structure about Fe shrinks slightly and the first neighbor Fe-Si bond length decreases by ≈ 0.05 Å . More importantly excess disorder is observed below 80–100 K (the coherence temperature T * ) in plots of the Debye-Waller factor σ 2 ( σ is the width of the pair distribution function); at low T the data deviate from the usual Einstein or correlated-Debye model plots. This excess disorder is most prominent for the Ru-Si bond, and σ 2 actually increases below 80 K. These results suggest a local orthorhombic distortion with B 1 g -like symmetry that develops below 80–100 K. A model that describes these local distortions is presented, and discussed in terms of other measurements that indicate a breaking of fourfold symmetry at low T . In addition, the square root of the difference between σ 2 ( T ) for the Ru-Si pair and a Debye fit to these data serves as an order parameter for this orthorhombic distortion, in the temperature range below 100 K. This quantity is a length related to a - b , the difference between the a and b lattice constants in the orthorhombic phase, and provides a connection between this distortion and T * . X-ray absorption near edge structure (XANES) measurements also show that there are no changes in the edge positions down to 0.1 eV for any edge as a function of x , for T in the HO regime.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Materials Data on SiRu2 by Materials Project

Ru2Si is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Ru2+ sites. In the first Ru2+ site, Ru2+ is bonded in a 5-coordinate geometry to five equivalent Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.47–2.88 Å. In the second Ru2+ site, Ru2+ is bonded in a 5-coordinate geometry to five equivalent Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.45–2.86 Å. Si4- is bonded in a 10-coordinate geometry to ten Ru2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si2Ru by Materials Project

RuSi2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ru is bonded in a body-centered cubic geometry to eight equivalent Si atoms. All Ru–Si bond lengths are 2.46 Å. Si is bonded to four equivalent Ru atoms to form a mixture of corner and edge-sharing SiRu4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on SiRu by Materials Project

RuSi crystallizes in the cubic P2_13 space group. The structure is three-dimensional. Ru4+ is bonded in a 7-coordinate geometry to seven equivalent Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.40–2.72 Å. Si4- is bonded in a 7-coordinate geometry to seven equivalent Ru4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si3Ru2 by Materials Project

Ru2Si3 is Magnesium tetraboride-like structured and crystallizes in the tetragonal P-4c2 space group. The structure is three-dimensional. there are three inequivalent Ru2+ sites. In the first Ru2+ site, Ru2+ is bonded in a 8-coordinate geometry to eight Si+1.33- atoms. There are four shorter (2.44 Å) and four longer (2.61 Å) Ru–Si bond lengths. In the second Ru2+ site, Ru2+ is bonded in a 6-coordinate geometry to six Si+1.33- atoms. There are four shorter (2.32 Å) and two longer (2.61 Å) Ru–Si bond lengths. In the third Ru2+ site, Ru2+ is bonded in a 6-coordinate geometry to eight Si+1.33- atoms. There are a spread of Ru–Si bond distances ranging from 2.35–2.89 Å. There are two inequivalent Si+1.33- sites. In the first Si+1.33- site, Si+1.33- is bonded in a 2-coordinate geometry to five Ru2+ atoms. In the second Si+1.33- site, Si+1.33- is bonded in a 4-coordinate geometry to five Ru2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si3Ru2 by Materials Project

Ru2Si3 crystallizes in the orthorhombic Pbcn space group. The structure is three-dimensional. there are three inequivalent Ru2+ sites. In the first Ru2+ site, Ru2+ is bonded in a 7-coordinate geometry to seven Si+1.33- atoms. There are a spread of Ru–Si bond distances ranging from 2.37–2.54 Å. In the second Ru2+ site, Ru2+ is bonded to six Si+1.33- atoms to form distorted edge-sharing RuSi6 octahedra. There are a spread of Ru–Si bond distances ranging from 2.33–2.48 Å. In the third Ru2+ site, Ru2+ is bonded in a 8-coordinate geometry to eight Si+1.33- atoms. There are a spread of Ru–Si bond distances ranging from 2.39–2.75 Å. There are three inequivalent Si+1.33- sites. In the first Si+1.33- site, Si+1.33- is bonded in a 4-coordinate geometry to four Ru2+ atoms. In the second Si+1.33- site, Si+1.33- is bonded in a 5-coordinate geometry to five Ru2+ atoms. In the third Si+1.33- site, Si+1.33- is bonded in a 5-coordinate geometry to five Ru2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on SiRu by Materials Project

RuSi is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ru4+ is bonded in a body-centered cubic geometry to eight equivalent Si4- atoms. All Ru–Si bond lengths are 2.55 Å. Si4- is bonded in a body-centered cubic geometry to eight equivalent Ru4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si3Ru4 by Materials Project

Ru4Si3 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are four inequivalent Ru3+ sites. In the first Ru3+ site, Ru3+ is bonded in a 5-coordinate geometry to five Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.43–2.79 Å. In the second Ru3+ site, Ru3+ is bonded in a 7-coordinate geometry to seven Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.52–2.66 Å. In the third Ru3+ site, Ru3+ is bonded in a distorted body-centered cubic geometry to eight Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.46–3.01 Å. In the fourth Ru3+ site, Ru3+ is bonded in a 6-coordinate geometry to six Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.41–2.85 Å. There are three inequivalent Si4- sites. In the first Si4- site, Si4- is bonded in a body-centered cubic geometry to eight Ru3+ atoms. In the second Si4- site, Si4- is bonded in a distorted body-centered cubic geometry to eight Ru3+ atoms. In the third Si4- site, Si4- is bonded in a 10-coordinate geometry to ten Ru3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Si2Ru by Materials Project

RuSi2 crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Ru is bonded in a body-centered cubic geometry to eight equivalent Si atoms. All Ru–Si bond lengths are 2.51 Å. Si is bonded in a 5-coordinate geometry to four equivalent Ru and one Si atom. The Si–Si bond length is 2.33 Å.

36 MATERIALS SCIENCE↗

Materials Data on Si3Ru5 by Materials Project

Ru5Si3 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. there are three inequivalent Ru+2.40+ sites. In the first Ru+2.40+ site, Ru+2.40+ is bonded to six Si4- atoms to form a mixture of distorted edge and corner-sharing RuSi6 octahedra. The corner-sharing octahedral tilt angles are 0°. There are four shorter (2.54 Å) and two longer (2.68 Å) Ru–Si bond lengths. In the second Ru+2.40+ site, Ru+2.40+ is bonded in a 5-coordinate geometry to five Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.39–2.77 Å. In the third Ru+2.40+ site, Ru+2.40+ is bonded in a 4-coordinate geometry to six Si4- atoms. There are a spread of Ru–Si bond distances ranging from 2.42–2.99 Å. There are two inequivalent Si4- sites. In the first Si4- site, Si4- is bonded in a body-centered cubic geometry to eight Ru+2.40+ atoms. In the second Si4- site, Si4- is bonded in a 10-coordinate geometry to ten Ru+2.40+ atoms.

36 MATERIALS SCIENCE↗