Structure and bonding in lithium ruthenate, Li2RuO3

James, Alison; Goodenough, John B

doi:10.1016/0022-4596(88)90357-x

Cited by 98 publications

(99 citation statements)

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“…Although transitions accompanied with the significant anomalies of χ and ρ similar to those of the present system, have been reported for La 4 6 octahedra, the similar mechanism has been discussed to understand their T dependent magnetic susceptibilities. [12][13][14][15] However, these systems do not exhibit a phase transition.…”

Section: )supporting

confidence: 79%

“…5,6) The powder neutron diffraction patterns of these samples indicate that a small amount of RuO 2 (molar fraction of ∼1.20 %) exists. There also exists an impurity peak of the unidentified phase, which has the integrated intensity of ~4.5 % of the maximum integrated intensity of the main phase as shown later.…”

Section: )mentioning

confidence: 96%

“…4) As one of possible examples of conductive electrons on honeycomb lattice, we have investigated physical properties of Li 2 RuO 3 . It has the layers of the honeycomb lattice of edge-sharing RuO 6 octahedra with a LiO 6 octahedron at the center of each hexagon of RuO 6 (Fig. 1).…”

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confidence: 99%

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New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure

et al. 2007

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A new-type structural transition has been found in Li 2 RuO 3 with honeycomb lattice of edge-sharing RuO 6 -octahedra. With decreasing temperature T, the electrical resistivity exhibits an anomalous increase at T=T c~5 40 K, suggesting the (metal to insulator)-like transition and the magnetic susceptibility also shows a sharp decrease. Detailed structure analyses have revealed that the high temperature space group C2/m changes to P2 1 /m at T c . The most striking fact is that a significant reduction of the bond lengths is found between two of six Ru-Ru pairs of the hexagon in the low temperature phase, indicating a new type phase transition by the mechanism of the formation of molecular orbits of these Ru-Ru pairs.KEYWORDS: Li 2 RuO 3 , honeycomb structure, structural transition *Corresponding author: e43247a@nucc.cc.nagoya-u.ac.jpCompounds with the honeycomb lattice often present interesting behavior originating from their characteristic structures. For example, in the course of the studies on the physical properties of localized spin systems of A 3 T 2 SbO 6 (A=Na, Li; T=Cu, Ni, Co) and Na 2 T 2 TeO 6 on the (distorted) honeycomb lattice, spin gap behaviors have been found for T=Cu, [1][2][3] while the magnetic transitions to the spin-ordered state have been observed for T=Co and Ni. 4)As one of possible examples of conductive electrons on honeycomb lattice, we have investigated physical properties of Li 2 RuO 3 . It has the layers of the honeycomb lattice of edge-sharing RuO 6 octahedra with a LiO 6 octahedron at the center of each hexagon of RuO 6 (Fig. 1). The Ru valence is +4 and the four electrons exist in the 4d t 2g orbits. For this system, we have found a phase transition at temperature T=T c~5 40 K, where the crystal symmetry changes from a monoclinic (space group C2/m) to another monoclinic (space group P2 1 /m) one with decreasing T. As described in detail later, the transition is associated with the molecular orbit formation of Ru 4+ -Ru 4+ ions of the edge-sharing RuO 6 pair, presenting a new mechanism of structural transitions.Polycrystalline samples of Li 2 RuO 3 were prepared by sintering pellets of mixtures of RuO 2 and Li 2 CO 3 with proper molar ratio at 1000 ˚C for 24 h in air. 5,6) The powder neutron diffraction patterns of these samples indicate that a small amount of RuO 2 (molar fraction of ∼1.20 %) exists. There also exists an impurity peak of the unidentified phase, which has the integrated intensity of ~4.5 % of the maximum integrated intensity of the main phase as shown later. The magnetic susceptibilities χ were measured using a Quantum Design SQUID magnetometer under a magnetic field H=1 T in the temperature range of 2-700 K. The electrical resistivities ρ were measured by the standard four-terminal method using an ac-resistance bridge from 4.6 K to 695 K. The specific heats C were measured by a thermal relaxation method in the temperature range of 5-60 K using a Physical Property Measurement System (PPMS, Quantum Design). Powder X-ray diffraction measurements were carrie...

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confidence: 79%

Section: )mentioning

confidence: 96%

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New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure

et al. 2007

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“…Initial reports on polycrystalline samples suggested a room temperature C2/c monoclinic structure and metallic paramagnetic behavior below T = 300 K [17][18][19] . Later a comprehensive study on polycrystalline samples of Li 2 RuO 3 revealed an unusual second order structural phase transition near T ≈ 540 K from a nearly perfect honeycomb lattice C2/m structure at high temperature to a low temperature structure with a distorted honeycomb lattice P2 1 /m 20 .…”

Section: Introductionmentioning

confidence: 99%

First-order magnetostructural transition in single crystals of the honeycomb lattice ruthenate Li2RuO3

Mehlawat¹,

Singh²

2017

Phys. Rev. B

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Li2RuO3 is known to crystallize in either C2/m or P 21/m structures at room temperature. We report the first single crystal growth of Li2RuO3 and Na substituted crystals (Li0.95Na0.05)2RuO3 crystallizing in the P 21/m structure where a magneto-structural transition is observed at high temperatures. Using high temperature (T ≤ 1000 K) magnetic susceptibility χ measurements we study the magnetic anisotropy across the magneto-structural transition. Our results show for the first time that for Li2RuO3 the magnetic and structural transitions most likely occur at slightly different temperatures. The structural transition which is first order-like occurs first (T ≈ 570 K) and drives the magnetic transition (T ≈ 540 K). Rather surprisingly, just 5% Na substitution for Li affects the magneto-structural transition in an interesting way. The first order transition temperature stays ≈ 540 K, the magnetic anisotropy is reversed, and the Ru-Ru dimerization pattern changes from two short and four long Ru-Ru bonds per honeycomb in an armchair pattern for Li2RuO3 to four short and two long bonds per honeycomb in (Li0.95Na0.05)2RuO3 which can be viewed as two inter-penetrating armchair patterns.

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“…Other examples of honeycomb-lattice compounds are A 2 RuO 3 (A = Li, Na) [13,[17][18][19] with nominally S =1 originating from Ru 4+ in the low-spin state. In contrast to A 2 IrO 3 (A = Li, Na), it has been discovered that Li 2 RuO 3 exhibits an unusual phase transition at T d ∼ 540 K [20].…”

Section: Introductionmentioning

confidence: 99%

Effect of disorder on the dimer transition of the honeycomb-lattice compoundLi2RuO3

et al. 2016

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We report the dependence of magnetic properties on the crystalline disorder in Li2RuO3 with Ru honeycomb lattice. This oxide exhibits unconventional Ru-dimer transition below T d ∼ 540 K. We demonstrate that the cell parameters, related to the coherence of the dimer formation, are strongly dependent on the synthesis procedure. We show that the magnetic behavior at the dimer transition is closely related to the lattice parameters. In particular, we revealed that samples with wellordered dimers exhibit a first-order magnetic transition with the onset exceeding 550 K, higher than that reported previously. We discuss possible dimer configurations leading to this magneto-lattice coupling.

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Structure and bonding in lithium ruthenate, Li2RuO3

Cited by 98 publications

References 14 publications

New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure

New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure

First-order magnetostructural transition in single crystals of the honeycomb lattice ruthenate Li2RuO3

Effect of disorder on the dimer transition of the honeycomb-lattice compoundLi2RuO3

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Structure and bonding in lithium ruthenate, Li2RuO3

Cited by 98 publications

References 14 publications

New-Type Phase Transition of Li2RuO3 with Honeycomb Structure

New-Type Phase Transition of Li2RuO3 with Honeycomb Structure

First-order magnetostructural transition in single crystals of the honeycomb lattice ruthenate Li2RuO3

Effect of disorder on the dimer transition of the honeycomb-lattice compoundLi2RuO3

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New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure

New-Type Phase Transition of Li₂RuO₃ with Honeycomb Structure