arXiv subjects

J. L. Musfeldt

Publications and source records attributed to J. L. Musfeldt.

At least 19 recordsLinked to original sources

arXiv2023

Spin-phonon interactions and magnetoelectric coupling in Co$_4$$B_2$O$_9$ ($B$ = Nb, Ta)

In order to explore the consequences of spin-orbit coupling on spin-phonon interactions in a set of chemically-similar mixed metal oxides, we measured the infrared vibrational properties of Co$_4B_2$O$_9$ ($B$ = Nb, Ta) as a function of temperature and compared our findings with lattice dynamics calculations and several different models of spin-phonon coupling. Frequency vs. temperature trends for the Co$^{2+}$ shearing mode near 150 cm$^{-1}$ reveal significant shifts across the magnetic ordering temperature that are especially large in relative terms. Bringing these results together and accounting for noncollinearity, we obtain spin-phonon coupling constants of -3.4 and -4.3 cm$^{-1}$ for Co$_4$Nb$_2$O$_9$ and the Ta analog, respectively. Analysis reveals that these coupling constants derive from interlayer (rather than intralayer) exchange interactions and that the interlayer interactions contain competing antiferromagnetic and ferromagnetic contributions. At the same time, beyond-Heisenberg terms are minimized due to fortuitous symmetry considerations, different than most other 4$d$- and 5$d$-containing oxides. Comparison with other contemporary oxides shows that spin-phonon coupling in this family of materials is among the strongest ever reported, suggesting an origin for magnetoelectric coupling.

cond-mat.mtrl-sci↗

arXiv2022

Nonreciprocal directional dichroism at telecom wavelengths

Magnetoelectrics with ultra-low symmetry and spin-orbit coupling are well known to display a number of remarkable properties including nonreciprocal directional dichroism. As a polar and chiral magnet, Ni$_3$TeO$_6$ is predicted to host this effect in three fundamentally different configurations, although only two have been experimentally verified. Inspired by the opportunity to unravel the structure-property relations of such a unique light-matter interaction, we combined magneto-optical spectroscopy and first-principles calculations to reveal nonreciprocity in the toroidal geometry and compared our findings with the chiral configurations. We find that formation of Ni toroidal moments is responsible for the largest effects near 1.1 eV - a tendency that is captured by our microscopic model and computational implementation. At the same time, we demonstrate deterministic control of nonreciprocal directional dichroism in Ni$_3$TeO$_6$ across the entire telecom wavelength range. This discovery will accelerate the development of photonics applications that take advantage of unusual symmetry characteristics.

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↗

arXiv2022

Vibrational fingerprints of ferroelectric hafnia

Hafnia (HfO2) is a promising material for emerging chip applications due to its high-k dielectric behaviour, suitability for negative capacitance heterostructures, scalable ferroelectricity, and silicon compatibility. The lattice dynamics along with phononic properties such as thermal conductivity, contraction, and heat capacity are under-explored, primarily due to the absence of high quality single crystals. Herein, we report the vibrational properties of a series of HfO2 crystals stabilized with yttrium (chemical formula HfO2:xY, where x = 20, 12, 11, 8, and 0%) and compare our findings with a symmetry analysis and lattice dynamics calculations. We untangle the effects of Y by testing our calculations against the measured Raman and infrared spectra of the cubic, antipolar orthorhombic, and monoclinic phases and then proceed to reveal the signature modes of polar orthorhombic hafnia. This work provides a spectroscopic fingerprint for several different phases of HfO2 and paves the way for an analysis of mode contributions to high-k dielectric and ferroelectric properties for chip technologies.

cond-mat.mtrl-sci↗

arXiv2020

Realization of the orbital-selective Mott state at the molecular level in Ba$_3$LaRu$_2$O$_9$

Molecular magnets based on heavy transition metals have recently attracted significant interest in the quest for novel magnetic properties. For systems with an odd number of valence electrons per molecule, high or low molecular spin states are typically expected in the double exchange or quasi-molecular orbital limits respectively. In this work, we use bulk characterization, muon spin relaxation, neutron diffraction, and inelastic neutron scattering to identify a rare intermediate spin-3/2 per dimer state in the 6H-perovskite Ba$_3$LaRu$_2$O$_9$ that cannot be understood in a double exchange or quasi-molecular orbital picture and instead arises from orbital-selective Mott insulating behavior at the molecular level. Our measurements are also indicative of collinear stripe magnetic order below $T_N$ = 26(1) K for these molecular spin-3/2 degrees-of-freedom, which is consistent with expectations for an ideal triangular lattice with significant next nearest neighbor in-plane exchange. Finally, we present neutron diffraction and Raman scattering data under applied pressure that reveal low-lying structural and spin state transitions at modest pressures P $\le$ 1 GPa, which highlights the delicate balance between competing energy scales in this system.

cond-mat.str-el↗

arXiv2019

Infrared nano-spectroscopy of ferroelastic domain walls in hybrid improper ferroelectric Ca$_3$Ti$_2$O$_7$

Ferroic materials are well known to exhibit heterogeneity in the form of domain walls. Understanding the properties of these boundaries is crucial for controlling functionality with external stimuli and for realizing their potential for ultra-low power memory and logic devices as well as novel computing architectures. In this work, we employ synchrotron-based near-field infrared nano-spectroscopy to reveal the vibrational properties of ferroelastic (90$^\circ$ ferroelectric) domain walls in the hybrid improper ferroelectric Ca$_3$Ti$_2$O$_7$. By locally mapping the Ti-O stretching and Ti-O-Ti bending modes, we reveal how structural order parameters rotate across a wall. Thus, we link observed near-field amplitude changes to underlying structural modulations and test ferroelectric switching models against real space measurements of local structure. This initiative opens the door to broadband infrared nano-imaging of heterogeneity in ferroics.

cond-mat.mtrl-sci↗

arXiv2009

Evaluation of Born and local effective charges in unoriented materials from vibrational spectra

We present an application of the Lorentz model in which fits to vibrational spectra or a Kramers Kronig analysis are employed along with several useful formalisms to quantify microscopic charge in unoriented (powdered) materials. The conditions under which these techniques can be employed are discussed, and we analyze the vibrational response of a layered transition metal dichalcogenide and its nanoscale analog to illustrate the utility of this approach.

cond-mat.mtrl-sci↗

arXiv2009

Spin-Charge-Lattice Coupling through Resonant Multi-Magnon Excitations in Multiferroic BiFeO3

Spin-charge-lattice coupling mediated by multi-magnon processes is demonstrated in multiferroic BiFeO3. Experimental evidence of two and three magnons excitations as well as multimagnon coupling at electronic energy scales and high temperatures are reported. Temperature dependent Raman experiments show up to five resonant enhancements of the 2-magnon excitation below the Neel temperature. These are shown to be collective interactions between on-site Fe d-d electronic resonance, phonons and multimagnons

cond-mat.other↗

arXiv2008

Charge order, dynamics, and magneto-structural transition in multiferroic LuFe$_2$O$_4$

We investigated the series of temperature and field-driven transitions in LuFe$_2$O$_4$ by optical and Mössbauer spectroscopies, magnetization, and x-ray scattering in order to understand the interplay between charge, structure, and magnetism in this multiferroic material. We demonstrate that charge fluctuation has an onset well below the charge ordering transition, supporting the "order by fluctuation" mechanism for the development of charge order superstructure. Bragg splitting and large magneto optical contrast suggest a low temperature monoclinic distortion that can be driven by both temperature and magnetic field.

cond-mat.str-el↗

arXiv2008

Correlation effects in the electronic structure of Mn$_4$ molecular magnet

We present joint theoretical-experimental study of the correlation effects in the electronic structure of (pyH)$_3$[Mn$_4$O$_3$Cl$_7$(OAc)$_3$]$\cdot$2MeCN molecular magnet (Mn$_4$). Describing the many-body effects by cluster dynamical mean-field theory, we find that Mn$_4$ is predominantly Hubbard insulator with strong electron correlations. The calculated electron gap (1.8 eV) agrees well with the results of optical conductivity measurements, while other methods, which neglect many-body effects or treat them in a simplified manner, do not provide such an agreement. Strong electron correlations in Mn$_4$ may have important implications for possible future applications.

cond-mat.mtrl-sci↗

arXiv2007

Infrared Investigation of the Charge Ordering Pattern in the Organic Spin Ladder Candidate (DTTTF)2Cu(mnt)2

We measured the variable temperature infrared response of the spin ladder candidate (DTTTF)2Cu(mnt)2 in order to distinguish between two competing ladder models, rectangular versus zigzag, proposed for this family of materials. The distortion along the stack direction below 235 K is consistent with a doubling along b through the metal-insulator transition. While this would agree with either of the ladder models, the concomitant transverse distortion rules out the rectangular ladder model and supports the zigzag scenario. Intramolecular distortions within the DTTTF building block molecule also give rise to on-site charge asymmetry.

cond-mat.other↗

arXiv2007

Pinned Low Energy Electronic Excitation in Metal Exchanged Vanadium Oxide Nanoscrolls

We measured the optical properties of mixed valent vanadium oxide nanoscrolls and their metal exchanged derivatives in order to investigate the charge dynamics in these compounds. In contrast to the prediction of a metallic state for the metal exchanged derivatives within a rigid band model, we find that the injected charges in Mn$^{2+}$ exchanged vanadium oxide nanoscrolls are pinned. A low-energy electronic excitation associated with the pinned carriers appears in the far infrared and persists at low temperature, suggesting that the nanoscrolls are weak metals in their bulk form, dominated by inhomogeneous charge disproportionation and Madelung energy effects.

cond-mat.mtrl-sci↗

arXiv2006

Optical Properties and Magnetic Field-Induced Phase Transitions in the Ferroelectric State of Ni$_3$V$_2$O$_8$

We use a combination of optical spectra, first principles calculations, and energy dependent magneto-optical measurements to elucidate the electronic structure and to study the phase diagram of Ni$_3$V$_2$O$_8$. We find a remarkable interplay of magnetic field and optical properties that reveals additional high magnetic field phases and an unexpected electronic structure which we associate with the strong magneto-dielectric couplings in this material over a wide energy range. Specifically, we observed several prominent magneto-dielectric effects that derive from changes in crystal field environment around Ni spine and cross-tie centers. This effect is consistent with a field-induced modification of local structure. Symmetry-breaking effects are also evident with temperature. We find Ni$_3$V$_2$O$_8$ to be an intermediate gap, local moment band insulator. This electronic structure is particularly favorable for magneto-dielectric couplings, because the material is not subject to the spin charge separation characteristic of strongly correlated large gap Mott insulators, while at the same time remaining a magnetic insulator independent of the particular spin order and temperature.

cond-mat.str-el↗

arXiv2006

Observation of 300 K High Energy MagnetoDielectric Response in the Bilayer Manganite (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$

We observed a large HEMD effect in the bilayer manganite (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$, a direct consequence of field driven spin-glass insulator to ferromagnetic metal transition. The remnants of the transition can be used to achieve dielectric contrast at room temperature. This discovery suggests that electronic mechanisms such as the metal-insulator transition, charge ordering, and orbital ordering can be exploited to give substantial dielectric contrast in other materials.

cond-mat.mtrl-sci↗

arXiv2006

Magneto-optical investigation of the field-induced spin-glass insulator to ferromagnetic metallic transition of the bilayer manganite (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$

We measured the magneto-optical response of (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$ in order to investigate the microscopic aspects of the magnetic field driven spin-glass insulator to ferromagnetic metal transition. Application of a magnetic field recovers the ferromagnetic state with an overall redshift of the electronic structure, growth of the bound carrier localization associated with ferromagnetic domains, development of a pseudogap, and softening of the Mn-O stretching and bending modes that indicate a structural change. We discuss field- and temperature-induced trends within the framework of the Tomioka-Tokura global electronic phase diagram picture and suggest that controlled disorder near a phase boundary can be used to tune the magnetodielectric response. Remnants of the spin-glass insulator to ferromagnetic metallic transition can also drive 300 K color changes in (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$.

cond-mat.str-el↗

arXiv2006

In Search of Microscopic Evidence for Molecular Level Negative Thermal Expansion in Fullerenes

We report the high-resolution far infrared vibrational properties of C60 and endohedral Kr@C60 fullerene as a function of temperature. Anomalous softening of the F1u(1) mode (526 cm-1) is observed throughout the temperature range of investigation (300 - 10 K) suggesting that the fullerene cage may expand at low temperature in these molecular solids. To test this idea, we combine these results with temperature and pressure dependent Raman, infrared, and Kr extended x-ray absorption fine structure data from the literature to provide a comprehensive view of local cage size effects. The results are consistent with a recent molecular dynamics study [Kwon et al., Phys. Rev. Lett. 92, 15901 (2004)] that predicts negative thermal expansion in carbon fullerenes.

cond-mat.mtrl-sci↗

arXiv2006

Magneto-Dielectric Effect in the S = 1/2 Quasi-Two Dimensional Antiferromagnet K2V3O8

We report the optical and magneto-optical properties of K2V3O8, an S=1/2 quasi-two-dimensional Heisenberg antiferromagnet. Local spin density approximation electronic structure calculations are used to assign the observed excitations and analyze the field dependent features. Two large magneto-optical effects, centered at ~1.19 and 2.5 eV, are attributed to field-induced changes in the V 4+ d to d on-site excitations due to modification of the local crystal field environment of the VO5 square pyramids with applied magnetic field. Taken together, the evidence for a soft lattice, the presence of vibrational fine structure on the sharp 1.19 eV magneto-optical feature,and the fact that these optical excitations are due to transitions from a nearly pure spin polarized V d state to hybridized states involving both V and O, suggest that the magneto-dielectric effect in K2V3O8 is driven by strong lattice coupling.

cond-mat.str-el↗

arXiv2006

Dynamics of Bulk vs. Nanoscale WS_2: Local Strain and Charging Effects

We measured the infrared vibrational properties of bulk and nanoparticle WS$_2$ in order to investigate the structure-property relations in these novel materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the \emph{xy}-polarized E$_{1u}$ vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.

cond-mat.mtrl-sci↗