Field-induced Structure Research Articles

Beyond the "spine of hydration": Chiral SFG spectroscopy detects DNA first hydration shell and base pair structures.

Experimental methods capable of selectively probing water at the DNA minor groove, major groove, and phosphate backbone are crucial for understanding how hydration influences DNA structure and function. Chiral-selective sum frequency generation spectroscopy (chiral SFG) is unique among vibrational spectroscopies because it can selectively probe water molecules that form chiral hydration structures around biomolecules. However, interpreting chiral SFG spectra is challenging since both water and the biomolecule can produce chiral SFG signals. Here, we combine experiment and computation to establish a theoretical framework for the rigorous interpretation of chiral SFG spectra of DNA. We demonstrate that chiral SFG detects the N-H stretch of DNA base pairs and the O-H stretch of water, exclusively probing water molecules in the DNA first hydration shell. Our analysis reveals that DNA transfers chirality to water molecules only within the first hydration shell, so they can be probed by chiral SFG spectroscopy. Beyond the first hydration shell, the electric field-induced water structure is symmetric and, therefore, precludes chiral SFG response. Furthermore, we find that chiral SFG can differentiate chiral subpopulations of first hydration shell water molecules at the minor groove, major groove, and phosphate backbone. Our findings challenge the scientific perspective dominant for more than 40 years that the minor groove "spine of hydration" is the only chiral water structure surrounding the DNA double helix. By identifying the molecular origins of the DNA chiral SFG spectrum, we lay a robust experimental and theoretical foundation for applying chiral SFG to explore the chemical and biological physics of DNA hydration.

Atomristor Mott Theory of Sn Adatom Adlayer on a Si Surface

We use a combination of density functional theory (DFT) and dynamical mean field theory (DMFT) to unveil orbital field-induced electronic structure reconstruction of the atomic Sn layer deposited onto a Si(111) surface (Sn/Si(111)−3×3R30∘), also referred to as α-Sn. Our DFT + DMFT results indicate that α-Sn is an ideal testing ground to explore electric field-driven orbital selectivity and Mott memory behavior, all arising from the close proximity of α-Sn to metal insulator transitions. We discuss the relevance of orbital phase changes for α-Sn in the context of the current–voltage (I−V) characteristic for future silicon-based metal semiconductor atomristors.

Electric field-induced electronic structure and intersubband transitions of a hydrogen molecular ion in a gaussian-type quantum ring

In this work, the influence of an external electric field on the electronic structure and intersubband transitions of a singly ionized double-donor system in a GaAs quantum ring defined by Gaussian-type potentials is investigated theoretically. Within the framework of the effective mass approach, the two-dimensional diagonalization method is used for the solution of the Schrödinger equation to obtain the eigen energies and corresponding wave functions. Numerical results reveal that the electronic energy spectrum and the linear optical absorption coefficient of the ring are remarkably affected by the strength of the lateral electric field, internuclear distance and parameters defining the confinement potential. Also, it has been shown that beyond the anti-crossing point, the wave functions exchange their symmetries without mixing, which is a characteristic feature of energy-level anti-crossing.

In-situ electric field-tailored exchange bias in the manganite/ferroelectric multiferroic heterostructures

The application of electric field-induced magnetic structure changes has significantly advanced nonvolatile data storage with ultralow energy consumption, as well as spintronics and quantum computing processes. In artificial perovskite oxide multiferroic structures composed of ferromagnetic and ferroelectric layers, the evolution of magnetic phases and ferroelectric domains often contribute to the magnetoelectric coupling. To fully understand the mechanisms behind electric field-induced changes in magnetic structures and enable the miniaturization of magnetoelectric devices, it is crucial to achieve local ferroelectric domain-triggered ferromagnetic evolution. In this study, we have fabricated La0.7Ca0.3MnO3/Pb(Zr0.52Ti0.48)O3 (LCMO/PZT) heterostructures, where the magnetic phase separation of LCMO and the ferroelectric domain of PZT can be modulated by substrates and piezoelectric force microscopy, respectively. Our experiments demonstrate that by switching the polarization states of PZT, we can observe electric field control of the magnetic exchange bias effect through changes in the phase separation of the LCMO layer. These results contribute to the development of magnetoelectric devices with enhanced properties and offer valuable insights for future design strategies.

Electrical Chain Rearrangement: What Happens When Polymers in Brushes Have a Charge Gradient?

Under the influence of electric fields, the chains in polyelectrolyte brushes can stretch and collapse, which changes the structure of the brush. Copolymer brushes with charged and uncharged monomers display a similar behavior. For pure polyelectrolyte and random copolymer brushes, the field-induced structure changes only the density of the brush and not its local composition, while the latter could be affected if charges are distributed inhomogeneously along the polymer backbone. Therefore, we systematically study the switching behavior of gradient polyelectrolyte brushes in electric fields for different solvent qualities, grafting densities, and charges per chain via coarse-grained molecular dynamics simulations. Similar to random copolymers and pure polyelectrolytes, these brushes show a mixed-phase transition: intermediate states between fully stretched and collapsed are characterized by a bimodal chain-end distribution. Additionally, we find that the total charge of the brush plays a key role in the critical field required for a complete transition. Finally, we find that gradient polyelectrolyte brushes are charge-enriched at the brush-solvent interface under stretched conditions and charge-depleted under collapsed conditions, allowing for control over the local composition and thus the surface charge of the brush due to the inhomogeneous charge along the grafted chains.

Unlocking Bimetallic Active Centers via Heterostructure Engineering for Exceptional Phosphate Electrosorption: Internal Electric Field-Induced Electronic Structure Reconstruction.

Development of electrode materials exhibiting exceptional phosphate removal performance represents a promising strategy to mitigate eutrophication and meet ever-stricter stringent emission standards. Herein, we precisely designed a novel LaCeOx heterostructure-decorated hierarchical carbon composite (L8C2PC) for high-efficiency phosphate electrosorption. This approach establishes an internal electric field within the LaCeOx heterostructure, where the electrons transfer from Ce atoms to neighboring La atoms through superexchange interactions in La-O-Ce coordination units. The modulatory heterostructure endows a positive shift of the d band of La sites and the increase of electron density at Fermi level, promoting stronger orbital overlap and binding interactions. The introduction of oxygen vacancies during the in situ nucleation process reduces the kinetic barrier for phosphate-ion migration and supplies additional active centers. Moreover, the hierarchical carbon framework ensures electrical double-layer capacitance for phosphate storage and interconnected ion migration channels. Such synergistically multiple active centers grant the L8C2PC electrode with high-efficiency record in phosphate electrosorption. As expected, the L8C2PC electrode demonstrates the highest removal capability among the reported electrode materials with a saturation capacity of 401.31 mg P g-1 and a dynamic capacity of 91.83 mg P g-1 at 1.2 V. This electrochemical system also performs well in the dephosphorization in natural water samples with low concentration that enable effluent concentration to meet the first-class discharge standard for China (0.5 mg P L-1). This study advances efficient dephosphorization techniques to a new level and offers a deep understanding of the internal electric field that regulates metal orbitals and electron densities in heterostructure engineering.

Ligand field luminescence in the honeycomb Mott insulator α-RuCl3

Novel electronic structure is central to Kitaev-like quantum spin liquid ground state in the van der Waals antiferromagnet α-RuCl3. In this octahedral low-spin system, the rich bandstructure includes Mott–Hubbard insulating bandgap of ∼1.1 eV and ligand field induced gap of ∼2 eV. Though the bandgap is extensively reported in previous optical and photoemission studies, the latter gap is less understood. In this regard, we probed the ligand field-induced electronic structure of bulk α-RuCl3 single crystals via unpolarized photoluminescence (PL) spectroscopy under linearly polarized excitation in the visible region. We observed the broad principal PL peak at E PL 1.87 eV, close to the energy required for the optical transition across the ligand field splitting gap (∼2 eV). This gap (E PL) monotonically increases with temperature, described by the thermal expansion of lattice parameters dominating the electron–phonon interaction in this Honeycomb Mott insulator. Moreover, we observed the multiplet structure of the PL spectra, which can be explained by parity-forbidden d–d transitions in the light of single ion ligand-field theory. We attribute the broad PL linewidths to strong vibronic coupling modeled by the Huang–Rhys parameter. Further we observed the signature of structural transitions, indicated by thermal hysteresis in normalized integrated PL intensity.

Giant electric field-induced strain and structure evolution of NaTaO3-modified 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 Pb-free ceramics

To acquire giant electric field-induced strain in non-Pb materials is attracting a great deal of attention in the past decade. In the current investigation, the crystal and domain structures as well as the electrical performances of (1-x) (0.94Bi0.5Na0.5TiO3-0.06BaTiO3)-xNaTaO3 (BNBT-xNT) specimens were systematically studied to achieve enhanced strain. The introduction of NT makes the phase structure transit from rhombohedral-tetragonal to pseudo-cubic structure. The original domain structure of BNBT is destroyed, and the disorder degree of the local structure increases. Simultaneously, the remnant polarization, coercive field, and piezoelectric coefficients were significantly decreased. The transition from ferroelectric to ergodic relaxation can be effectively modified, thus lowering the transition zone to room temperature. Finally, the BNBT-3NT ceramics achieve marked strain coefficients at room temperature, with a maximum strain of 0.394% under 65 kV/cm and a d33* of 606 pm/V.

Superior Energy-Storage Properties in Bi0.5Na0.5TiO3-Based Lead-Free Ceramics via Simultaneously Manipulating Multiscale Structure and Field-Induced Structure Transition.

Pratical applications have put forward great challenges to the comprehensive energy-storage performance of ceramic material. Here, a novel route of simultaneously manipulating multiscale structure and the field-induced structural transformation in (Bi0.5Na0.5)TiO3-based ceramics is proposed to address the above concern. The multiscale structure of 0.88(Bi0.5Na0.5)TiO3-0.12BaTiO3 solid solutions such as grain and domain size, band gap, and phase structure can be adjusted by adding antiferroelectric NaNbO3. Simultaneously, a field-induced P4bm relaxor antiferroelectric to P4mm ferroelectric phase transformation can be obtained by constructing a P4mm-P4bm phase boundary, which is expected to require a lower energy barrier compared with the field-induced P4bm relaxor antiferroelectric to R3c ferroelectric transformation in other (Bi0.5Na0.5)TiO3-based ceramics. The optimized field-induced structural transformation behavior and the formation of nanodomains enables a minimized polarization hysteresis but an enhanced maximum polarization. Moreover, the decreased grain size together with increased band gap leads to a significantly improved breakdown strength. Accordingly, a giant energy density Wrec ∼ 8.0 J/cm3, a high efficiency η ∼ 86%, a short discharging time t0.9 ∼ 41 ns, and a good temperature stability (Wrec = 1.32 ± 0.12 J/cm3, η = 88.5% ± 2.5% @ 25-200 °C) are simultaneously obtained in 0.63(Bi0.5Na0.5)TiO3-0.12BaTiO3-0.25NaNbO3 relaxor antiferroelectric ceramics, demonstrating large potentials for the ceramic capacitor applications.

Field-induced heterophase state in PbZrO3 thin films

Applications of epitaxial antiferroelectrics face scientific challenges, such as limited understanding of degraded (in comparison to bulk) switching behavior and its relation to nanoscale structural organization. We report on an unusual structural response of ${\mathrm{PbZrO}}_{3}/{\mathrm{SrRuO}}_{3}/{\mathrm{SrTiO}}_{3}$ (001) heterostructures to precritical (lower than required for switching) electric fields. In situ x-ray diffraction shows a ferrielectric-like structure, which forms gradually upon increasing the applied field and makes up a heterophase state with the host antiferroelectric phase. The field-induced structure is similar to the antiferroelectric parent phase in the octahedral-tilt pattern, but differs from it in the lead-ion displacement pattern. The latter can be encoded as $\ensuremath{\uparrow}\ensuremath{\uparrow}\ensuremath{\uparrow}\ensuremath{\uparrow}\phantom{\rule{4pt}{0ex}}\ensuremath{\downarrow}\ensuremath{\uparrow}\ensuremath{\uparrow}\ensuremath{\downarrow}$ provided that the antiferroelectric structure is encoded as $\ensuremath{\downarrow}\ensuremath{\downarrow}\ensuremath{\uparrow}\ensuremath{\uparrow}$. We propose that the unusual commensurateness (as opposed to the more ubiquitous incommensuration in similar materials) between the modulation periods of host and guest phases can be explained by accounting for the energy of heterophase boundaries, which is important in dense nanostructures due to the high surface-to-bulk ratio of nanodomains. An analysis using the ab-initio-correlated, but empirical (parametrized) energy model suggests that the observed field-induced structure is likely to be selected in ${\mathrm{PbZrO}}_{3}$ instead of the others in the case when the above commensuration effect is at play. The results point to the mechanism leading to the smearing of polarization-field loops in such heterostructures and suggest a perspective for the controlled creation of delicate dipolar orderings for ferroic-based memory.

Field-induced topological Hall effect in antiferromagnetic axion insulator candidate EuIn2As2

Magnetic topological materials have attracted significant attention due to their potential realization of a variety of novel quantum phenomena. ${\mathrm{EuIn}}_{2}{\mathrm{As}}_{2}$ has recently been theoretically recognized as a long-awaited intrinsic antiferromagnetic bulk axion insulator. However, experimental studies of the transport properties arising from the topological states in this material are scarce. In this paper, we perform detailed magnetoresistance (MR) and Hall measurements to study the magnetotransport properties of this material. We find that the transport is strongly influenced by the spin configuration of the Eu moments from the concomitant change in the field dependence of the MR and that of the magnetization below the N\'eel temperature. Most importantly, an anomalous Hall effect (AHE) and a large topological Hall effect (THE) are observed. We suggest that the AHE is originated from a nonvanishing net Berry curvature due to the helical spin structure and that the THE is attributed to the formation of a noncoplanar spin texture with a finite scalar spin chirality induced by the external magnetic field in ${\mathrm{EuIn}}_{2}{\mathrm{As}}_{2}$. Our studies provide a platform to understand the influence of the interplay between the topology of electronic bands and the field-induced magnetic structure on magnetoelectric transport properties. In addition, our observations give a hint to realize axion insulator states and higher-order topological insulator states through manipulating the magnetic state of ${\mathrm{EuIn}}_{2}{\mathrm{As}}_{2}$.

Anisotropic magnetic liquid metal film for wearable wireless electromagnetic sensing and smart electromagnetic interference shielding

Smart and wearable electromagnetic (EM) functional materials that can reasonably use EM energy and prevent EM pollution are of great significance to the future information society, but their design and preparation are still challenging. Here, a multifunctional EM response film is prepared based on a magnetic liquid metal droplet-filled elastomer with magnetic field-induced anisotropic structure, which can reversibly construct conductive network and tune heterogeneous interface during cyclic stretching. This film can withstand up to 600% tensile strain and shows stretching-enhanced electrical conductivity. Its EM interference shielding effectiveness (SE) significantly increases with stretching, and the relative SE change (ΔSE/SE0) shows a linear response to the tensile strain. The specific shielding effectiveness (an ultrahigh value of 404 dB mm−1 at 400% strain) and strain sensitivity of the film outperform other stretchable EM functional materials. More interestingly, this film exhibits rapid switching between EM wave transmission and shielding through continuous stretching, which enables an off/on switchable EM interference shielding function. Furthermore, it can be used in a wearable EM sensor to wirelessly monitor human movements by recording changes of EM wave intensity.

Interplay between charge density wave order and magnetic field in the nonmagnetic rare-earth tritelluride LaTe3

Charge density wave (CDW) states in solids bear an intimate connection to underlying fermiology. Modification of the latter by a suitable perturbation provides an attractive handle to unearth novel CDW states. Here, we combine extensive magnetotransport experiments and first-principles electronic structure calculations on a non-magnetic tritelluride LaTe$_{3}$ single crystal to uncover phenomena rare in CDW systems: $(i)$ hump-like feature in the temperature dependence of resistivity at low temperature under application of magnetic field, which moves to higher temperature with increasing field strength, $(ii)$ highly anisotropic large transverse magnetoresistance (MR) upon rotation of magnetic field about current parallel to crystallographic c-axis, (iii) anomalously large positive MR with spike-like peaks at characteristic angles when the angle between current and field is varied in the bc-plane, (iv) extreme sensitivity of the angular variation of MR on field and temperature. Moreover, our Hall measurement reveals remarkably high carrier mobility $\sim$ 33000 cm$^{2}$/Vs, which is comparable to that observed in some topological semimetals. These novel observations find a comprehensive explication in our density functional theory (DFT) and dynamical mean field theory (DMFT) calculations that capture field-induced electronic structure modification in LaTe$_{3}$. The band structure theory together with transport calculations suggest the possibility of a second field-induced CDW transition from the field-reconstructed Fermi surface, which qualitatively explains the hump in temperature dependence of resistivity at low temperature. Thus, our study exposes the novel manifestations of the interplay between CDW order and field-induced electronic structure modifications in LaTe$_{3}$, and establishes a new route to tune CDW states by perturbations like magnetic field.

Three-dimensional ferromagnetism and magnetotransport in van der Waals Mn-intercalated tantalum disufide

Van der Waals (vdW) ferromagnets are an important class of materials for spintronics applications. The recent discovery of atomically vdW magnets CrI$_3$ and Cr$_2$Ge$_2$Te$_6$ has triggered a renaissance in the area of two-dimensional (2D) magnetism. Herein we systematically studied 2H-Mn$_{0.28}$TaS$_2$ single crystal, a 2D vdW ferromagnet with $T_c$ $\sim$ 82.3 K and a large in-plane magnetic anisotropy. Mn $K$-edge x-ray absorption spectroscopy was measured to provide information on its electronic state and local atomic environment. The detailed magnetic isotherms measured in the vicinity of $T_c$ indicates that the spin coupling inside 2H-Mn$_{0.28}$TaS$_2$ is of a three-dimensional (3D) Heisenberg-type coupled with the attractive long-range interaction between spins that decay as $J(r)\approx r^{-4.85}$. Both resistivity $\rho(T)$ and thermopower $S(T)$ exhibit anomalies near $T_c$, confirming that the hole-type transport carriers strongly interact with local moments. An unusual angle-dependent magnetoresistance is further observed, suggesting a possible field-induced novel magnetic structure.

Variety of scenarios for magnetic exchange response in topological insulators

We present an ab initio relativistic k.p theory of the effect of magnetic exchange field on the band structure in the gap region of bulk crystals and thin films of three-dimensional layered topological insulators. For the field perpendicular to the layers (along $z$), we reveal novel unconventional scenarios of the response of the band-gap edges to the magnetization. The modification of the valence and conduction states is considered in terms of their $\Gamma$-point spin $s^z$ and total angular momentum $J^z$ on the atomic sites where the states are localized. The actual scenario depends on whether $s^z$ and $J^z$ have the same or opposite sign. In particular, the opposite sign for the valence state and the same sign for the conduction state give rise to an unconventional response in Bi$_2$Te$_3$ -- both in the bulk crystal and in ultra-thin films, which fundamentally distinguishes this topological insulator from Bi$_2$Se$_3$, where both states have the same sign. To gain a deeper insight into different scenarios in insulators with both inverted and non-inverted zero-field band structure, a minimal four-band third-order k.p model is constructed from first principles. Within this model, we analyze the field-induced band structure of the insulators and identify Weyl nodes that appear in a magnetic phase and behave differently depending on the scenario. We characterize the topology of the modified band structure by the Chern number $\mathcal{C}$ and find the unconventional response to be accompanied by a large Chern number $\mathcal{C}=\pm3$.

Field-induced topological Hall effect and double-fan spin structure with a c-axis component in the metallic kagome antiferromagnetic compound YMn6Sn6.

Geometric frustration in the kagome lattice makes it a great host for the flat electronic band, nontrivial topological properties, and novel magnetism. Here, we use magnetotransport measurements to map out the field-temperature phase diagram of the centrosymmetric YMn6Sn6 with a Mn kagome lattice and show that the system exhibits the topological Hall effect (THE) with an in-plane applied magnetic field around 240 K. In addition, our neutron diffraction results demonstrate that the observed THE cannot arise from a magnetic skyrmion lattice, but instead from an in-plane field-induced double-fan spin structure with -axis components. This paper provides a platform to understand the influence of a field-induced novel magnetic structure on magnetoelectric response in topological kagome metals.

Two coupled chains are simpler than one: field-induced chirality in a frustrated spin ladder

Although the frustrated (zigzag) spin chain is the Drosophila of frustrated magnetism, our understanding of a pair of coupled zigzag chains (frustrated spin ladder) in a magnetic field is still lacking. We address this problem through nuclear magnetic resonance (NMR) experiments on BiCu_2PO_6 in magnetic fields up to 45 T, revealing a field-induced spiral magnetic structure. Conjointly, we present advanced numerical calculations showing that even a moderate rung coupling dramatically simplifies the phase diagram below half-saturation magnetization by stabilizing a field-induced chiral phase. Surprisingly for a one-dimensional model, this phase and its response to Dzyaloshinskii-Moriya (DM) interactions adhere to classical expectations. While explaining the behavior at the highest accessible magnetic fields, our results imply a different origin for the solitonic phases occurring at lower fields in BiCu_2PO_6. An exciting possibility is that the known, DM-mediated coupling between chirality and crystal lattice may give rise to a new kind of spin-Peierls instability.

Field-induced magnetic phase transitions and the resultant giant anomalous Hall effect in the antiferromagnetic half-Heusler compound DyPtBi

We report field-induced magnetic phase transitions and transport properties of antiferromagnetic DyPtBi. We show that DyPtBi hosts a delicate balance between two different magnetic ground states, which can be controlled by a moderate magnetic field. Furthermore, it exhibits giant anomalous Hall effect (\sigma_A=1540 (ohm cm)^{-1},\theta_{AHE} = 24%) in a field-induced Type-I spin structure, presumably attributed to the enhanced Berry curvature associated with avoided band-crossings near the Fermi energy and / or non-zero spin chirality. The latter mechanism points DyPtBi towards a rare potential realization of anomalous Hall effect in an antiferromagnet with face-center-cubic lattice that was proposed in [Physical Review Letters 87, 116801 (2001)].

Janus monolayer PtSSe under external electric field and strain: A first principles study on electronic structure and optical properties

Abstract The effect of biaxial strains e b and electric field E on the electronic structure and optical properties of Janus monolayer PtSSe was studied by Density Functional Theory (DFT). A reasonable band gap of PtSSe was found to be 1.547 eV. In the infrared region, both biaxial strains and electric fields result in noticeable enhancement of the electronic structure as well as optical properties of PtSSe. Especially, under biaxial strains, the change of PtSSe band gap obeys the form of an asymmetric concave down parabola. This result confirms the existence of a maximum PtSSe band gap under biaxial strains e b and the possibility of tuning PtSSe band gap to fit the requirement of the optoelectronic devices. The absorption rate in the visible light region of Janus monolayer PtSSe increases sharply and can be altered by strain engineering. Biaxial strain not only alters the absorption intensity but can also significantly shift the position of these absorption peaks. The present study provides additional information about the strain and electric field-induced electronic structure and optical properties of Janus monolayer PtSSe, which should be taken into account for better PtSSe-based devices.

Silica anchored colloidal suspension of magnetite nanorods

This study focuses on the interaction of colloidal silica nanoparticles with the magnetite (Fe3O4) magnetic fluids (MF), which eventually forms nanorod like structure. The aqueous magnetic fluid consists of magnetite nanoparticles having double layers of lauric acid surfactant. This surfactant provides stability towards short-range van der Waals attractive and steric repulsive forces, as well as long-range dipole-dipole interactive force. Whereas, in the colloidal silica, the sodium ions provide stability to the silica nanoparticles. The colloidal silica and magnetic fluid both were mixed in different proportions to understand the interaction between the silica and magnetite nanoparticles. Thus, the interaction present in the system is studied using FTIR, TGA, and magnetic field induced microscopy. The FTIR and TGA data reveal that silica interacts with the outer layer of lauric acid through the Si–O bond and eventually provides stability to the system. The length of the lauric acid sheath varies with the concentration of silica nanoparticles. The SEM images indicate nanorod formation, and its structure dimensions vary with the silica concentrations, which is also reflected in the magnetic field-induced structure formations. The structure observed using microscopy correlated with the interaction derived from FTIR and TGA data analysis. XRD data of iron oxide (magnetite) nanoparticles are present here again for completion.