Valence of cerium ions in selected ternary compounds from the system Ce-Rh-Sn

Over the last years, intermetallic compounds from the system Ce–Rh–Sn have attracted a considerable attention owing to a rich variety of strongly correlated electron phenomena they exhibit. CeRhSn2, Ce5Rh4Sn10, Ce2Rh3Sn5 and Ce3Rh4Sn13 are magnetically ordered heavy fermion systems [1-5]. Interestingly, for Ce3+xRh4Sn13-x (0.2<x<0.6) no sign of Kondo effect and long range magnetic order was found down to the temperature of 0.4 K [5]. In turn, CeRhSn shows non-Fermi liquid-type thermodynamic and transport properties at low temperatures [6-7] accompanied by an intermediate valence state of the Ce ions. Further, for CeRhSn, CeRhSn2 and CeRh2Sn4 spin fluctuations due to the Rh 4d electrons were also suggested [1,7-8]. The possible coexistence of magnetic phenomena originating from Ce and Rh makes the unequivocal interpretation of experimental data for these compounds very difficult. Consequently, a detailed understanding of the very complex physical properties/behavior requires the use of a broad spectrum of experimental methods, including extended thermodynamic and transport measurements as well as careful investigations of electronic structure. For these systems the full characterization of Ce 4f states in regard to their occupancy, localization in a conduction band and hybridization with the other valence band states is crucial for an unambiguous determination of ground state properties and the low energy excitations. Thus, X-ray absorption spectroscopy (XAS) is here of great use as a bulk probe which is highly sensitive on chemical states of elements. Furthermore, absorption measurements at the Ce LIII edge results in spectra with minimized lifetime broadening, largely unaffected by complicated many-electron final state effects. These spectra can be used to estimate the numbers for the fractional valence of Ce which originates from the strong hybridization between the Ce 4f and the other valence band states related to the valence fluctuation phenomena and/or to the formation of covalent bonds

Local magnetism in MnSiPt rules the chemical bond

A crystal structure can be understood as a result of bonding interactions (covalent, ionic, van der Waals, etc.) between the constituting atoms. If the forces caused by these interactions are equilibrated, the so-stabilized crystal structure should have the lowest energy. In such an atomic configuration, additional weaker atomic interactions may further reduce the total energy, influencing the final atomic arrangement. Indeed, in the intermetallic compound MnSiPt, a 3D framework is formed by polar covalent bonds between Mn, Si, and Pt atoms. Without taking into account the local spin polarization of manganese atoms, they would form Mn–Mn bonds within the framework. Surprisingly, the local magnetic moments of manganese prevent the formation of Mn–Mn bonds, thus changing decisively and significantly the final atomic arrangement.Among intermetallic compounds, ternary phases with the simple stoichiometric ratio 1:1:1 form one of the largest families. More than 15 structural patterns have been observed for several hundred compounds constituting this group. This, on first glance unexpected, finding is a consequence of the complex mechanism of chemical bonding in intermetallic structures, allowing for large diversity. Their formation process can be understood based on a hierarchy of energy scales: The main share is contributed by covalent and ionic interactions in accordance with the electronic needs of the participating elements. However, smaller additional atomic interactions may still tip the scales. Here, we demonstrate that the local spin polarization of paramagnetic manganese in the new compound MnSiPt rules the adopted TiNiSi-type crystal structure. Combining a thorough experimental characterization with a theoretical analysis of the energy landscape and the chemical bonding of MnSiPt, we show that the paramagnetism of the Mn atoms suppresses the formation of Mn–Mn bonds, deciding between competing crystal structures

Pressure-induced reconstructive phase transition in Cd3As2

Cadmium arsenide Cd3As2 hosts massless Dirac electrons in its ambient-conditions tetragonal phase. We report X-ray diffraction and electrical resistivity measurements of Cd3As2 upon cycling pressure beyond the critical pressure of the tetragonal phase and back to ambient conditions. We find that at room temperature the transition between the low- and high-pressure phases results in large microstrain and reduced crystallite size both on rising and falling pressure. This leads to non-reversible electronic properties including self-doping associated with defects and a reduction of the electron mobility by an order of magnitude due to increased scattering. Our study indicates that the structural transformation is sluggish and shows a sizable hysteresis of over 1 GPa. Therefore, we conclude that the transition is first-order reconstructive, with chemical bonds being broken and rearranged in the high-pressure phase. Using the diffraction measurements we demonstrate that annealing at ~200 deg. C greatly improves the crystallinity of the high-pressure phase. We show that its Bragg peaks can be indexed as a primitive orthorhombic lattice with a_HP = 8.68 Å, b_HP = 17.15 Å and c_HP = 18.58 Å. The diffraction study indicates that during the structural transformation a new phase with another primitive orthorhombic structure may be also stabilized by deviatoric stress, providing an additional venue for tuning the unconventional electronic states in Cd3As2

Complex magnetic phase diagram of metamagnetic MnPtSi.

The magnetic, thermal and transport properties as well as electronic band structure of MnPtSi are reported. MnPtSi is a metal that undergoes a ferromagnetic transition at T_C = 340(1) K and a spin–reorientation transition at T_N = 326(1) K to an antiferromagnetic phase. First–principles electronic structure calculations indicate a not–fully polarized spin state of Mn in a d^5 electron configuration with J = S = 3/2, in agreement with the saturation magnetization of 3 µ_B per f.u. in the ordered state and the observed paramagnetic effective moment. A sizeable anomalous Hall effect in the antiferromagnetic phase alongside the computational study suggests that the antiferromagnetic structure is noncollinear. Based on thermodynamic measurements and resistivity data we construct a magnetic phase diagram. Magnetization curves M(H) at low temperatures reveal a metamagnetic transition of spin–flop type. The spin-flopped phase terminates at a critical point with T_cr ≈ 300 K and H_cr ≈ 10 kOe, near which a peak of the magnetocaloric entropy change is observed. Using Arrott plot analysis and magnetoresistivity data we argue that the metamagnetic transition is of a first–order type, whereas the strong field dependence of T_N and the linear relationship of the T_N with M^2 hint at its magnetoelastic nature

Complex magnetic phase diagram of metamagnetic MnPtSi

The magnetic, thermal and transport properties as well as electronic band structure of MnPtSi are reported. MnPtSi is a metal that undergoes a ferromagnetic transition at T_C = 340(1) K and a spin–reorientation transition at T_N = 326(1) K to an antiferromagnetic phase. First–principles electronic structure calculations indicate a not–fully polarized spin state of Mn in a d^5 electron configuration with J = S = 3/2, in agreement with the saturation magnetization of 3 µ_B per f.u. in the ordered state and the observed paramagnetic effective moment. A sizeable anomalous Hall effect in the antiferromagnetic phase alongside the computational study suggests that the antiferromagnetic structure is non–collinear. Based on thermodynamic measurements and resistivity data we construct a magnetic phase diagram. Magnetization curves M(H) at low temperatures reveal a metamagnetic transition of spin–flop type. The spin-flopped phase terminates at a critical point with T_cr ≈ 300 K and H_cr ≈ 10 kOe, near which a peak of the magnetocaloric entropy change is observed. Using Arrott plot analysis and magnetoresistivity data we argue that the metamagnetic transition is of a first–order type, whereas the strong field dependence of T_N and the linear relationship of the T_N with M^2 hint at its magnetoelastic nature

Alloy design by tailoring phase stability in commercial Ti alloys.

The mechanical characteristics and the operative deformation mechanisms of a metallic alloy can be optimised by explicitly controlling phase stability. Here an integrated thermoelastic and pseudoelastic model is presented to evaluate the β stability in Ti alloys. The energy landscape of β→α′/α'' martensitic transformation was expressed in terms of the dilatational and transformational strain energy, the Gibbs free energy change, the external mechanical work as well as the internal frictional resistance. To test the model, new alloys were developed by tailoring two base alloys, Ti–6Al–4V and Ti–6Al–7Nb, with the addition of β-stabilising element Mo. The alloys exhibited versatile mechanical behaviours with enhanced plasticity. Martensitic nucleation and growth was fundamentally dominated by the competition between elastic strain energy and chemical driving force, where the latter term tends to lower the transformational energy barrier. The model incorporates thermodynamics and micromechanics to quantitatively investigate the threshold energy for operating transformation-induced plasticity and further guides alloy desig

Field-induced double dome and Bose-Einstein condensation in the crossing quantum spin chain system AgVOAsO4

We present inelastic neutron scattering data on the quantum paramagnet AgVOAsO4 that establish the system is a S=1/2 alternating spin chain compound and provide a direct measurement of the spin gap. We also present experimental evidence for two different types of field-induced magnetic order between μ0Hc1= 8.4 T and μ0Hc2=48.9 T, which may be related to Bose-Einstein condensation (BEC) of triplons. Thermodynamic measurements in magnetic fields up to 60 T and temperatures down to 0.1 K reveal a H−T phase diagram consisting of a dome encapsulating two ordered phases with maximum ordering temperatures of 3.8 K and 5.3 K respectively. This complex phase diagram is not expected for a single-Q BEC system and therefore establishes AgVOAsO4 as a promising multi-Q BEC candidate capable of hosting exotic vortex phases

Carbon Dots/Iron Oxide Nanoparticles with Tuneable Composition and Properties

We present a simple strategy to generate a family of carbon dots/iron oxide nanoparticles (C/Fe-NPs) that relies on the thermal decomposition of iron (III) acetylacetonate in the presence of a highly fluorescent carbon-rich precursor (derived via thermal treatment of ethanolamine and citric acid at 180 °C), while polyethylene glycol serves as the passivation agent. By varying the molar ratio of the reactants, a series of C/Fe-NPs have been synthesized with tuneable elemental composition in terms of C, H, O, N and Fe. The quantum yield is enhanced from 6 to 9% as the carbon content increases from 27 to 36 wt%, while the room temperature saturation magnetization is improved from 4.1 to 17.7 emu/g as the iron content is enriched from 17 to 31 wt%. In addition, the C/Fe-NPs show excellent antimicrobial properties, minimal cytotoxicity and demonstrate promising bioimaging capabilities, thus showing great potential for the development of advanced diagnostic tools

Truncated mass divergence in a Mott metal

The Mott metal–insulator transition represents one of the most fundamental phenomena in condensed matter physics. Yet, basic tenets of the canonical Brinkman-Rice picture of Mott localization remain to be tested experimentally by quantum oscillation measurements that directly probe the quasiparticle Fermi surface and effective mass. By extending this technique to high pressure, we have examined the metallic state on the threshold of Mott localization in clean, undoped crystals of NiS2. We find that i) on approaching Mott localization, the quasiparticle mass is strongly enhanced, whereas the Fermi surface remains essentially unchanged; ii) the quasiparticle mass closely follows the divergent form predicted theoretically, establishing charge carrier slowdown as the driver for the metal–insulator transition; iii) this mass divergence is truncated by the metal–insulator transition, placing the Mott critical point inside the insulating section of the phase diagram. The inaccessibility of the Mott critical point in NiS2 parallels findings at the threshold of ferromagnetism in clean metallic systems, in which criticality at low temperature is almost universally interrupted by first-order transitions or novel emergent phases such as incommensurate magnetic order or unconventional superconductivity