arXiv subjects

M. J. Gutmann

Publications and source records attributed to M. J. Gutmann.

At least 19 recordsLinked to original sources

arXiv2025

Intrinsic disorder in the candidate quantum spin ice Pr$_2$Zr$_2$O$_7$

Quantum spin liquids with long-range entanglement are of great interest for applications in quantum technology. The quantum spin ice Pr$_2$Zr$_2$O$_7$ is a promising example, where it is believed that structural disorder plays a key role in enhancing quantum mechanical effects by introducing strains that split the ground state doublet akin to the effect of a local disordered transverse field. However, the precise defect structure responsible for this behaviour is unknown. Here we have determined the intrinsic defect structure of Pr$_2$Zr$_2$O$_7$ using neutron and x-ray scattering techniques supported by density functional theory. We find the main defect is the stuffing of Zr$^{4+}$ sites by Pr$^{3+}$ ions, accompanied by charge compensating O$^{2-}$ vacancies, and the relaxation of a neighbouring O$^{2-}$ ion to an interstitial site. Our results explain the single-ion magnetism by considering the non-magnetic singlets that arise on neighbouring sites as a result of the defect structure. These singlets account for additional features in the crystal electric field excitations. The effects caused by this low level of structural disorder are magnified since several neighbouring Pr sites are affected. This makes a significant contribution towards the observed broadening of pinch points in the magnetic diffuse scattering, which was previously attributed purely to quantum effects.

cond-mat.str-el↗

arXiv2023

Magnetic properties of the layered heavy fermion antiferromagnet CePdGa$_6$

We report the magnetic properties of the layered heavy fermion antiferromagnet CePdGa$_{6}$, and their evolution upon tuning with the application of magnetic field and pressure. CePdGa$_{6}$ orders antiferromagnetically below $T\rm_{N}$ = 5.2 K, where there is evidence for heavy fermion behavior from an enhanced Sommerfeld coefficient. Our results are best explained by a magnetic ground state of ferromagnetically coupled layers of Ce $4f$-moments orientated along the $c$-axis, with antiferromagnetic coupling between layers. At low temperatures we observe two metamagnetic transitions for fields applied along the $c$-axis corresponding to spin-flip transitions, where the lower transition is to a different magnetic phase with a magnetization one-third of the saturated value. From our analysis of the magnetic susceptibility, we propose a CEF level scheme which accounts for the Ising anisotropy at low temperatures, and we find that the evolution of the magnetic ground state can be explained considering both antiferromagnetic exchange between nearest neighbor and next nearest neighbor layers, indicating the influence of long-range interactions. Meanwhile we find little change of $T\rm_{N}$ upon applying hydrostatic pressures up to 2.2 GPa, suggesting that significantly higher pressures are required to examine for possible quantum critical behaviors.

cond-mat.str-el↗

arXiv2022

Fast broadband cluster spin-glass dynamics in PbFe$_{1/2}$Nb$_{1/2}$O$_{3}$

PbFe$_{1/2}$Nb$_{1/2}$O$_{3}$ (PFN) is a relaxor ferroelectric (T$_{c}$ $\sim$ 400 K) consisting of disordered magnetic Fe$^{3+}$ (S=${5\over2}$, L$\approx$0) ions resulting in a low temperature ``cluster glass" phase (W. Kleemann $\textit{et al.}$ Phys. Rev. Lett. ${\bf{105}}$, 257202 (2010)). We apply neutron scattering to investigate the dynamic magnetism of this phase in a large single crystal which displays a low temperature spin glass transition (T$_{g} \sim$ 15 K), but no observable spatially long-range antiferromagnetic order. The static response in the cluster glass phase (sampled on the timescale set by our resolution) is found to be characterized by an average magnetic spin direction that lacks any preferred direction. The dynamics that drive this phase are defined by a magnetic correlation length that gradually increases with decreasing temperature. However, below $\sim$ 50 K the spatial correlations gradually becoming more short range indicative of increasing disorder on cooling, thereby unravelling magnetism, until the low temperature glass phase sets in at T$_{g}$ $\sim$ 15 K. Neutron spectroscopy is used to characterize the spin fluctuations in the cluster glass phase and are found to be defined by a broadband of frequencies on the scale of $\sim$ THz, termed here ``fast" fluctuations. The frequency bandwidth driving the magnetic fluctuations mimics the correlation length and decreases until $\sim$ 50 K, and then increases again until the glass transition. Through investigating the low-energy acoustic phonons we find evidence of multiple distinct structural regions which form the basis of the clusters, generating a significant amount of local disorder. We suggest that random molecular fields originating from conflicting interactions between clusters is important for the destruction of magnetic order and the eventual formation of the cluster glass in PFN.

cond-mat.mtrl-sci↗

arXiv2022

Band-Mott mixing hybridizes the gap in Fe$_2$Mo$_3$O$_8$

We combined optical spectroscopy and first principles electronic structure calculations to reveal the charge gap in the polar magnet Fe$_2$Mo$_3$O$_8$. Iron occupation on the octahedral site draws the gap strongly downward compared to the Zn parent compound, and subsequent occupation of the tetrahedral site creates a narrow resonance near the Fermi energy that draws the gap downward even further. This resonance is a many-body effect that emanates from a flat valence band in a Mott-like state due to screening of the local moment - similar to expectations for a Zhang-Rice singlet, except that here, it appears in a semi-conductor. We discuss the unusual hybridization in terms of orbital occupation and character as well as the structure-property relationships that can be unveiled in various metal-substituted systems (Ni, Mn, Co, Zn).

cond-mat.str-el↗

arXiv2021

Nodeless superconductivity in Lu$_{5-x}$Rh$_6$Sn$_{18+x}$ with broken time reversal symmetry

Evidence for broken time reversal symmetry (TRS) has been found in the superconducting states of the $R_5$Rh$_6$Sn$_{18}$ (R = Sc, Y, Lu) compounds with a centrosymmetric caged crystal structure, but the origin of this phenomenon is unresolved. Here we report neutron diffraction measurements of single crystals with $R$=Lu, as well as measurements of the temperature dependence of the magnetic penetration depth using a self-induced tunnel diode-oscillator (TDO) based technique, together with band structure calculations using density functional theory. Neutron diffraction measurements reveal that the system crystallizes in a tetragonal caged structure, and that one of nominal Lu sites in the Lu$_5$Rh$_6$Sn$_{18}$ structure is occupied by Sn, yielding a composition Lu$_{5-x}$Rh$_6$Sn$_{18+x}$ ($x=1$). The low temperature penetration depth shift $Δλ(T)$ exhibits an exponential temperature dependence below around $0.3T_c$, giving clear evidence for fully gapped superconductivity. The derived superfluid density is reasonably well accounted for by a single gap $s$-wave model, whereas agreement cannot be found for models of TRS breaking states with two-component order parameters. Moreover, band structure calculations reveal multiple bands crossing the Fermi level, and indicate that the aforementioned TRS breaking states would be expected to have nodes on the Fermi surface, in constrast to the observations.

cond-mat.supr-con↗

arXiv2019

Spectroscopic and first principle DFT+eDMFT study of complex structural, electronic, and vibrational properties of $M_2$Mo$_3$O$_8$ ($M$=Fe, Mn) polar magnets

Optical spectroscopy, X-ray diffraction measurements, density functional theory (DFT) and density functional theory + embedded dynamical mean field theory (DFT+eDMFT) have been used to characterize structural and electronic properties of hexagonal $M_2$Mo$_3$O$_8$ ($M$=Fe, Mn) polar magnets. Our experimental data are consistent with the room temperature structure belonging to the space group P6$_3$mc for both compounds. The experimental structural and electronic properties at room temperature are well reproduced within DFT+eDMFT method, thus establishing its predictive power in the paramagnetic phase. With decreasing temperature, both compounds undergo a magnetic phase transition and we argue that this transition is concurrent with a structural phase transition (symmetry change from P6$_3$mc) in the Fe compound and an isostructural transition (no symmetry change from P6$_3$mc) in the Mn compound. In addition, the unusual temperature dependent behavior of electronic d-d transitions in Fe$^{2+}$ ions is discussed.

cond-mat.str-el↗

arXiv2019

Commensurate to incommensurate magnetic phase transition in Honeycomb-lattice pyrovanadate Mn2V2O7

We have synthesized single crystalline sample of Mn$_2$V$_2$O$_7$ using floating zone technique and investigated the ground state using magnetic susceptibility, heat capacity and neutron diffraction. Our magnetic susceptibility and heat capacity reveal two successive magnetic transitions at $T_{N1} =$ 19 K and $T_{N2} =$ 11.8 K indicating two distinct magnetically ordered phases. The single crystal neutron diffraction study shows that in the temperature ($T$) range 11.8 K $\le T \le$ 19 K the magnetic structure is commensurate with propagation vector $k_1 = (0, 0.5, 0)$, while upon lowering temperature below $T_{N2} =$ 11.8 K an incommensurate magnetic order emerges with $k_2 = (0.38, 0.48, 0.5)$ and the magnetic structure can be represented by cycloidal modulation of the Mn spin in $ac-$plane. We are reporting this commensurate to incommensurate transition for the first time. We discuss the role of the magnetic exchange interactions and spin-orbital coupling on the stability of the observed magnetic phase transitions.

cond-mat.str-el↗

arXiv2019

Role of defects in determining the magnetic ground state of ytterbium titanate

Pyrochlore systems are ideally suited to the exploration of geometrical frustration in three dimensions, and their rich phenomenology encompasses topological order and fractional excitations. Classical spin ices provide the first context in which it is possible to control emergent magnetic monopoles, and anisotropic exchange leads to even richer behaviour associated with large quantum fluctuations. Whether the magnetic ground state of Yb2Ti2O7 is a quantum spin liquid or a ferromagnetic phase induced by a Higgs transition appears to be sample dependent. Here we have determined the role of structural defects on the magnetic ground state via the diffuse scattering of neutrons. We find that oxygen vacancies stabilise the spin liquid phase and the stuffing of Ti sites by Yb suppresses it. Samples in which the oxygen vacancies have been eliminated by annealing in oxygen exhibit a transition to a ferromagnetic phase, and this is the true magnetic ground state.

cond-mat.str-el↗

arXiv2018

Persistence of antiferromagnetic order upon La substitution in the $4d^4$ Mott insulator Ca$_2$RuO$_4$

The chemical and magnetic structures of the series of compounds Ca$_{2-x}$La$_x$RuO$_4$ [$x = 0$, $0.05(1)$, $0.07(1)$, $0.12(1)$] have been investigated using neutron diffraction and resonant elastic x-ray scattering. Upon La doping, the low temperature S-Pbca space group of the parent compound is retained in all insulating samples [$x\leq0.07(1)$], but with significant changes to the atomic positions within the unit cell. These changes can be characterised in terms of the local RuO$_6$ octahedral coordination: with increasing doping the structure, crudely speaking, evolves from an orthorhombic unit cell with compressed octahedra to a quasi-tetragonal unit cell with elongated ones. The magnetic structure on the other hand, is found to be robust, with the basic $k=(0,0,0)$, $b$-axis antiferromagnetic order of the parent compound preserved below the critical La doping concentration of $x\approx0.11$. The only effects of La doping on the magnetic structure are to suppress the A-centred mode, favouring the B mode instead, and to reduce the Néel temperature somewhat. Our results are discussed with reference to previous experimental reports on the effects of cation substitution on the $d^4$ Mott insulator Ca$_2$RuO$_4$, as well as with regard to theoretical studies on the evolution of its electronic and magnetic structure. In particular, our results rule out the presence of a proposed ferromagnetic phase, and suggest that the structural effects associated with La substitution play an important role in the physics of the system.

cond-mat.str-el↗

arXiv2015

Vacancy defects and monopole dynamics in oxygen-deficient pyrochlores

The idea of magnetic monopoles in spin ice has enjoyed much success at intermediate temperatures, but at low temperatures a description in terms of monopole dynamics alone is insufficient. Recently, numerical simulations were used to argue that magnetic impurities account for this discrepancy by introducing a magnetic equivalent of residual resistance in the system. Here we propose that oxygen deficiency is the leading cause of magnetic impurities in as-grown samples, and we determine the defect structure and magnetism in Y2Ti2O(7-δ) using diffuse neutron scattering and magnetization measurements. These defects are eliminated by oxygen annealing. The introduction of oxygen vacancies causes Ti4+ to transform to magnetic Ti3+ with quenched orbital magnetism, but the concentration is anomalously low. In the spin-ice material Dy2Ti2O7 we find that the same oxygen-vacancy defects suppress moments on neighbouring rare-earth sites, and that these magnetic distortions dramatically slow down the long-time monopole dynamics at sub-Kelvin temperatures.

cond-mat.str-el↗

arXiv2015

Structural and Magnetic Investigations of Single-Crystals of the Neodymium Zirconate Pyrochlore, Nd2Zr2O7

We report structural and magnetic properties studies of large high quality single-crystals of the frustrated magnet, Nd$_2$Zr$_2$O$_7$. Powder x-ray diffraction analysis confirms that Nd$_2$Zr$_2$O$_7$ adopts the pyrochlore structure. Room-temperature x-ray diffraction and time-of-flight neutron scattering experiments show that the crystals are stoichiometric in composition with no measurable site disorder. The temperature dependence of the magnetic susceptibility shows no magnetic ordering at temperatures down to 0.5 K. Fits to the magnetic susceptibility data using a Curie-Weiss law reveal a ferromagnetic coupling between the Nd moments. Magnetization versus field measurements show a local Ising anisotropy along the <111> axes of the Nd$^{3+}$ ions in the ground state. Specific heat versus temperature measurements in zero applied magnetic field indicate the presence of a thermal anomaly below $T\sim7$ K, but no evidence of magnetic ordering is observed down to 0.5 K. The experimental temperature dependence of the single-crystal bulk dc susceptibility and isothermal magnetization are analyzed using crystal field theory and the crystal field parameters and exchange coupling constants determined.

cond-mat.str-el↗

arXiv2015

Divacancy superstructures in thermoelectric calcium-doped sodium cobaltate

We have grown single crystals of Na$_x$Ca$_y$CoO$_2$ and determined their superstructures as a function of composition using neutron and x-ray diffraction. Inclusion of Ca$^{2+}$ stabilises a single superstructure across a wide range of temperatures and concentrations. The superstructure in the Na$^+$ layers is based on arrays of divacancy clusters with Ca$^{2+}$ ions occupying the central site, and it has an ideal concentration Na$_{4/7}$Ca$_{1/7}$CoO$_2$. Previous measurements of the thermoelectric properties on this system are discussed in light of this superstructure. Na$_{4/7}$Ca$_{1/7}$CoO$_2$ corresponds to the maximum in thermoelectric performance of this system.

cond-mat.str-el↗

arXiv2015

Two-dimensional Cs-vacancy superstructure in iron-based superconductor $Cs_{0.8}Fe_{1.6}Se_2$

Single crystal neutron diffraction is combined with synchrotron x-ray scattering to identify the different superlattice phases present in $Cs_{0.8}Fe_{1.6}Se_2$. A combination of single crystal refinements and first principles modelling are used to provide structural solutions for the $\sqrt{5}\times\sqrt{5}$ and $\sqrt{2}\times\sqrt{2}$ superlattice phases. The $\sqrt{5}\times\sqrt{5}$ superlattice structure is predominantly composed of ordered Fe vacancies and Fe distortions, whereas the $\sqrt{2}\times\sqrt{2}$ superlattice is composed of ordered Cs vacancies. The Cs vacancies only order within the plane, causing Bragg rods in reciprocal space. By mapping x-ray diffraction measurements with narrow spatial resolution over the surface of the sample, the structural domain pattern was determined, consistent with the notion of a majority antiferromagnetic $\sqrt{5}\times\sqrt{5}$ phase and a superconducting $\sqrt{2}\times\sqrt{2}$ phase.

cond-mat.supr-con↗

arXiv2013

Dimerization-Induced Cross-Layer Quasi-Two-Dimensionality in Metallic Iridate IrTe2

The crystal structure of layered metal IrTe2 is determined using single-crystal x-ray diffraction. At T=220 K, it exhibits Ir and Te dimers forming a valence-bond crystal. Electronic structure calculations reveal an intriguing quasi-two-dimensional electronic state, with planes of reduced density of states cutting diagonally through the Ir and Te layers. These planes are formed by the Ir and Te dimers, which exhibit a signature of covalent bonding character development. Evidence for significant charge disproportionation among the dimerized and non-dimerized Ir (charge order) is also presented.

cond-mat.str-el↗

arXiv2013

Room temperature single-crystal diffuse scattering and ab initio lattice dynamics in CaTiSiO5

Single-crystal diffuse scattering data have been collected at room temperature on synthetic titanite using both neutrons and high-energy X-rays. A simple ball-and-springs model reproduces the observed diffuse scattering well, confirming its origin to be primarily due to thermal motion of the atoms. Ab initio phonons are calculated using density-functional perturbation theory and are shown to reproduce the experimental diffuse scattering. The observed X-ray and neutron scattering patterns are consistent with a summation of mode frequencies and displacement eigenvectors associated with the entire phonon spectrum, rather than with a simple, short-range static displacement. A band gap is observed between 600 and 700 cm-1 with only two modes crossing this region, both associated with antiferroelectric Ti-O motion along a. One of these modes (of Bu symmetry), displays a large LO-TO mode-splitting (562-701.4 cm-1) and has a dominant component coming from Ti-O bond stretching and, thus, the mode-splitting is related to the polarizability of the Ti-O bonds along the chain direction. Similar mode-splitting is observed in piezo- and ferroelectric materials. The calculated phonon dispersion model may be of use to others in the future to understand the phase transition at higher temperatures, as well as in the interpretation of measured phonon dispersion curves.

cond-mat.mtrl-sci↗

arXiv2011

The magnetic and crystal structure of azurite Cu$_3$(CO$_3$)$_2$(OH)$_2$ as determined by neutron diffraction

Here we present neutron diffraction results on the mineral azurite. We have found that the crystal structure of azurite can be described in the space group $P2_1$ which is the next lower symmetric group of $P2_1/c$ as found in earlier work. This small change in symmetry does not greatly influence the lattice parameters or atomic fractional coordinates which are presented here for single crystal diffraction refinements. The ordered magnetic moment structure of this material has been determined and is comprised of two inequivalent magnetic moments on copper sites of magnitude 0.68(1) and 0.25(1) $μ_{B}$. This result is discussed in terms of the anisotropic exchange and Dzyaloshinskii-Moriya interactions. It is found that the system is likely governed by one-dimensional behaviour despite the long-range ordered ground state. We also highlight the significance of strain in this material which is strongly coupled to the magnetism.

cond-mat.str-el↗

arXiv2009

Crystal-to-stripe reordering of sodium ions in NaxCoO2 (x>=0.75)

The sodium reordering in NaxCoO2 in the vicinity of room temperature is rationalized at high x in terms of phase transitions between square and striped phases. A striking hexagon-of-hexagons diffraction pattern observed for x=0.78 can be reproduced using coexisting square and striped phases that are related by simple shear deformations. All compositions exhibit a partial melting transition to a disordered stripe phase just below room temperature, which alters the topology of the electrical conduction pathways.

cond-mat.str-el↗

arXiv2007

Patterning of sodium ions and the control of electrons in sodium cobaltate

NaxCoO2 has emerged as a material of exceptional scientific interest due to the potential for thermoelectric applications, and because the strong interplay between the magnetic and superconducting properties has led to close comparisons with the physics of the high-Tc cuprates. The density, x, of the sodium in the intercalation layers can be altered electrochemically, directly changing the number of conduction electrons on triangular Co layers. Recent electron diffraction measurements reveal a kaleidoscope of Na+ ion patterns as a function of concentration. Here we use single-crystal neutron diffraction supported by numerical simulations to determine the long-range three-dimensional superstructures of these ions. We show that the sodium ordering and its associated distortion field are governed by pure electrostatics, and the organizational principle is the stabilization of charge droplets that order long range at some simple fractional fillings. Our results provide a good starting point to understand the electronic properties in terms of a Hubbard Hamiltonian taking into account the electrostatic potential from the Na superstructures. The resulting depth of potential wells in the Co layer is greater than the single-particle hopping kinetic energy. As a consequence, holes occupy preferentially the lowest potential regions and, therefore, the Na+ ion patterning plays a decisive role in the transport and magnetic properties.

cond-mat.str-el↗