Spin-State Transition and Metal-Insulator Transition in La1−x_{1-x}Eux_xCoO3_3}

We present a study of the structure, the electric resistivity, the magnetic susceptibility, and the thermal expansion of La$_{1-x}$Eu$_x$CoO$_3$. LaCoO$_3$ shows a temperature-induced spin-state transition around 100 K and a metal-insulator transition around 500 K. Partial substitution of La$^{3+}$ by the smaller Eu$^{3+}$ causes chemical pressure and leads to a drastic increase of the spin gap from about 190 K in LaCoO$_3$ to about 2000 K in EuCoO$_3$, so that the spin-state transition is shifted to much higher temperatures. A combined analysis of thermal expansion and susceptibility gives evidence that the spin-state transition has to be attributed to a population of an intermediate-spin state with orbital order for $x<0.5$ and without orbital order for larger $x$. In contrast to the spin-state transition, the metal-insulator transition is shifted only moderately to higher temperatures with increasing Eu content, showing that the metal-insulator transition occurs independently from the spin-state distribution of the Co$^{3+}$ ions. Around the metal-insulator transition the magnetic susceptibility shows a similar increase for all $x$ and approaches a doping-independent value around 1000 K indicating that well above the metal-insulator transition the same spin state is approached for all $x$.Comment: 10 pages, 6 figure

Spin state and phase competition in TbBaCo_{2}O_{5.5} and the lanthanide series LnBaCo_{2}O_{5+\delta} (0<=\delta<=1)

A clear physics picture of TbBaCo$_{2}$O$_{5.5}$ is revealed on the basis of density functional theory calculations. An antiferromagnetic (AFM) superexchange coupling between the almost high-spin Co$^{3+}$ ions competes with a ferromagnetic (FM) interaction mediated by both p-d exchange and double exchange, being responsible for the observed AFM-FM transition. And the metal-insulator transition is accompanied by an xy/xz orbital-ordering transition. Moreover, this picture can be generalized to the whole lanthanide series, and it is predicted that a few room-temperature magnetoresistance materials could be found in LnBa$_{1-x}$A$_{x}$Co$_{2}$O$_{5+\delta}$ (Ln=Ho,Er,Tm,Yb,Lu; A=Sr,Ca,Mg).Comment: 13 pages, 2 figures; to be published in Phys. Rev. B on 1st Sept. Title and Bylines are added to the revised versio

Optimisation of three-dimensional lower jaw resection margin planning using a novel Black Bone magnetic resonance imaging protocol

Background MRI is the optimal method for sensitive detection of tumour tissue and pre-operative staging in oral cancer. When jawbone resections are necessary, the current standard of care for oral tumour surgery in our hospital is 3D virtual planning from CT data. 3D printed jawbone cutting guides are designed from the CT data. The tumour margins are difficult to visualise on CT, whereas they are clearly visible on MRI scans. The aim of this study was to change the conventional CT-based workflow by developing a method for 3D MRI-based lower jaw models. The MRI-based visualisation of the tumour aids in planning bone resection margins. Materials and findings A workflow for MRI-based 3D surgical planning with bone cutting guides was developed using a four-step approach. Key MRI parameters were defined (phase 1), followed by an application of selected Black Bone MRI sequences on healthy volunteers (phase 2). Three Black Bone MRI sequences were chosen for phase 3: standard, fat saturated, and an out of phase sequence. These protocols were validated by applying them on patients (n = 10) and comparison to corresponding CT data. The mean deviation values between the MRI-and the CT-based models were 0.63, 0.59 and 0.80 mm for the three evaluated Black Bone MRI sequences. Phase 4 entailed examination of the clinical value during surgery, using excellently fitting printed bone cutting guides designed from MRI-based lower jaw models, in two patients with oral cancer. The mean deviation of the resection planes was 2.3 mm, 3.8 mm for the fibula segments, and the mean axis deviation was the fibula segments of 1.9 E. Conclusions This study offers a method for 3D virtual resection planning and surgery using cutting guides based solely on MRI imaging. Therefore, no additional CT data are required for 3D virtual planning in oral cancer surgery

Evidence for orbital ordering in LaCoO3

We present powder and single crystal X-ray diffraction data as evidence for a monoclinic distortion in the low spin (S=0) and intermediate spin state (S=1) of LaCoO3. The alternation of short and long bonds in the ab plane indicates the presence of eg orbital ordering induced by a cooperative Jahn-Teller distortion. We observe an increase of the Jahn-Teller distortion with temperature in agreement with a thermally activated behavior of the Co3+ ions from a low-spin ground state to an intermediate-spin excited state.Comment: Accepted to Phys. Rev.

Magnetic resonance imaging assessment of renal flow distribution patterns during ex vivo normothermic machine perfusion in porcine and human kidneys

Acceptance criteria of deceased donor organs have gradually been extended toward suboptimal quality, posing an urgent need for more objective pre-transplant organ assessment. Ex vivo normothermic machine perfusion (NMP) combined with magnetic resonance imaging (MRI) could assist clinicians in deciding whether a donor kidney is suitable for transplantation. Aim of this study was to characterize the regional distribution of perfusate flow during NMP, to better understand how ex vivo kidney assessment protocols should eventually be designed. Nine porcine and 4 human discarded kidneys underwent 3 h of NMP in an MRI-compatible perfusion setup. Arterial spin labeling scans were performed every 15 min, resulting in perfusion-weighted images that visualize intrarenal flow distribution. At the start of NMP, all kidneys were mainly centrally perfused and it took time for the outer cortex to reach its physiological dominant perfusion state. Calculated corticomedullary ratios based on the perfusion maps reached a physiological range comparable to in vivo observations, but only after 1 to 2 h after the start of NMP. Before that, the functionally important renal cortex appeared severely underperfused. Our findings suggest that early functional NMP quality assessment markers may not reflect actual physiology and should therefore be interpreted with caution

Strongly Coupled Magnetic and Electronic Transitions in Multivalent Strontium Cobaltites

The topotactic phase transition in SrCoOx (x = 2.5-3.0) makes it possible to reversibly transit between the two distinct phases, i.e. the brownmillerite SrCoO2.5 that is a room-temperature antiferromagnetic insulator (AFM-I) and the perovskite SrCoO3 that is a ferromagnetic metal (FM-M), owing to their multiple valence states. For the intermediate x values, the two distinct phases are expected to strongly compete with each other. With oxidation of SrCoO2.5, however, it has been conjectured that the magnetic transition is decoupled to the electronic phase transition, i.e., the AFM-to-FM transition occurs before the insulator-to-metal transition (IMT), which is still controversial. Here, we bridge the gap between the two-phase transitions by density-functional theory calculations combined with optical spectroscopy. We confirm that the IMT actually occurs concomitantly with the FM transition near the oxygen content x = 2.75. Strong charge-spin coupling drives the concurrent IMT and AFM-to-FM transition, which fosters the near room-T magnetic transition characteristic. Ultimately, our study demonstrates that SrCoOx is an intriguingly rare candidate for inducing coupled magnetic and electronic transition via fast and reversible redox reactions

Ligand-hole localization in oxides with unusual valence Fe

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes

The Magnetoelectric Effect in Transition Metal Oxides: Insights and the Rational Design of New Materials from First Principles

The search for materials displaying a large magnetoelectric effect has occupied researchers for many decades. The rewards could include not only advanced electronics technologies, but also fundamental insights concerning the dielectric and magnetic properties of condensed matter. In this article, we focus on the magnetoelectric effect in transition metal oxides and review the manner in which first-principles calculations have helped guide the search for (and increasingly, predicted) new materials and shed light on the microscopic mechanisms responsible for magnetoelectric phenomena.Comment: 24 pages, 12 figure