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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO 2

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. We find that this high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO 2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Spin-lattice dynamics of surface vs core magnetization in Fe nanoparticles

Magnetization of clusters is often simulated using atomistic spin dynamics for a fixed lattice. Coupled spinlattice dynamics simulations of the magnetization of nanoparticles have up to now neglected the change in the size of the atomic magnetic moments near surfaces. We show that the introduction of variable magnetic moments leads to a better description of experimental data for the magnetization of small Fe nanoparticles. To this end we divide atoms into a surface-near shell and a core with bulk properties. Here, it is demonstrated that both the magnitude of the shell magnetic moment and the exchange interactions need to be modified to obtain a fair representation of the experimental data. This allows for a reasonable description of the average magnetic moment versus cluster size, and also the cluster magnetization versus temperature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Geometric integration of classical spin dynamics via a mean-field Schrödinger equation

The Landau-Lifshitz equation describes the time evolution of magnetic dipoles and can be derived by taking the classical limit of a quantum mechanical spin Hamiltonian. To take this limit, one constrains the many-body quantum state to a tensor product of coherent states, thereby neglecting entanglement between sites. Expectation values of the quantum spin operators produce the usual classical spin dipoles. One may also consider expectation values of polynomials of the spin operators, leading to quadrupole and higher-order spin moments, which satisfy a dynamical equation of motion that generalizes the Landau-Lifshitz dynamics [Zhang and Batista, Phys. Rev. B 104, 104409 (2021)]. Here we reformulate the dynamics of these N 2 –1 generalized spin components as a mean-field Schrödinger equation on the N-dimensional coherent state. Furthermore, this viewpoint suggests efficient integration methods that respect the local symplectic structure of the classical spin dynamics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Order fractionalization in a Kitaev-Kondo model

We describe a mechanism for order fractionalization in a two-dimensional Kondo lattice model, in which electrons interact with a gapless spin liquid of Majorana fermions described by the Yao-Lee (YL) model. When the Kondo coupling to the conduction electrons exceeds a critical value, the model develops a superconducting instability into a state with a a spinor order parameter with charge 4 and spin ( = 1 2. The broken symmetry state develops a gapless Majorana Dirac cone in the bulk. By including an appropriate gauge string, we can show that the charge 4, spinorial order develops off-diagonal long range order that allows electrons to coherently tunnel arbitrarily long distances through the spin liquid.

36 MATERIALS SCIENCE↗

Observation of orbital selective charge transfer in a Fe/BaTi⁢O 3 interfacial two-dimensional electron gas

Two-dimensional electron gas (2DEG) states at oxide interfaces between two ferroic materials have been fertile ground to realize controllable multiferroicity. Here, in this work, we investigate the 2DEG states at the interface of ferroelectric BaTi⁢O 3 and a magnetic layer of iron using angle-resolved photoemission spectroscopy. Orbital-selective charge transfer occurs on the surprisingly robust 2DEG. Based on first-principles calculations, we show how the interfacial hybridization can give rise to the unexpected charge transfer in the magnetic 2DEG. Our study reveals a close interplay on a 2DEG between magnetic and ferroelectric interfaces, which sheds light on future design principles of multiferroic 2DEG states.

36 MATERIALS SCIENCE↗

Synthesis and Observation of Emergent Phenomena in Epitaxial Heusler Compound Heterostructures

The proposal was on the synthesis and observation of emergent phenomena in epitaxial Heusler compound heterostructures. The large range of properties and number of Heusler compounds opens up a wide number of potential compounds that will exhibit emergent phenomena. The similarity, large range of relatively inexpensive, large area, high crystal quality, III-V bulk substrates, lattice parameters and the ability to tune the lattice parameters through ternary or quaternary III-V compound semiconductor epitaxial growth, makes III-V semiconductors an ideal choice for substrates for epitaxial growth of Heusler compounds. A number of half Heusler compounds have been predicted to exhibit band inversion, making them topological and are therefore expected to exhibit spin-momentum locked topological surface states with linear dispersion. Others are predicted to be semimetals with Weyl points and others semiconducting and magnetic. During the course of this grant, emphasis has been on investigating Heusler compounds with emergent phenomena and demonstrating the ability to tune their properties through alloying and strain. We have grown toplogical semimetal (PtLuSb, PtMnBi), Weyl (Co 2 MnAl, Co 2 TiGe), half metal (PtMnSb, Co 2 MnSi, Co 2 MnAl x Si 1-x , Co2FeAl), and semiconducting (CoTiSb, NiTiSn) and tuned their properties through alloying and epitaxial strain. We also investigated the closely related materials of rare-earth monopnictide, some of which have also been predicted to be topological. During the attempts to grow the PtMnBi, it was discovered that Bi, another predicted topological material when ultrathin, could be grown epitaxially on InSb, results for which are also reported here. The main focus for this effort has been on using variable photon energy and spin-dependent angle resolved photoemission (ARPES) to determine bulk band structure and surface states of pristine epitaxial films grown on III-V semiconductor and MgO substrates and correlate results with theory and transport measurements. Theory has been critical to interpretation of experimental results and has been essential in guiding experiments. The research benefited from several strong collaborations between the PIs and the beamline scientists at the Advanced Light Source at Lawrence Berkeley Laboratory, the Stanford Linear Accelerator Center (SLAC) at Stanford and at the Max Lab at Lund University in Sweden. The strong experiment - theory collaboration between the PI’s groups, the Palmstrøm group at UCSB and the Janotti group at the University of Delaware, has been critical for interpreting the experimental ARPES and magnetotransport measurements results and making predictions to guide experiments. Weekly interactive Zoom meetings made this work well. A collaboration between the Palmstrøm group and Dr. Alexei Fedorov at the Advanced Light Source (ALS) resulted in significant modifications to his end chamber to accommodate the vacuum suitcase that was designed and constructed in the Palmstrøm group at UCSB. In collaboration with beamline scientists, Drs. Makoto Hashimoto and Donghui Lu at SLAC, Palmstrøm made modifications to the vacuum suitcase and developed special sample holders that allowed samples to be grown in the Palmstrøm MBE systems at UCSB and transported in the UHV vacuum suitcase to SLAC for ARPES measurements. The development of the vacuum suitcase was essential for this grant as it has allowed variable photon energies to be used to identify surface versus bulk states on samples that could not be capped and decapped using As- or Sb-capping layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Topics in atomic hydrogen standard research and applications

Hydrogen maser based frequency and time standards have been in continuous use at NASA tracking stations since February 1970, while laboratory work at Goddard has continued in the further development and improvement of hydrogen masers. Concurrently, experimental work has been in progress with a new frequency standard based upon the hydrogen atom using the molecular beam magnetic resonance method. Much of the hydrogen maser technology is directly applicable to the new hydrogen beam standard, and calculations based upon realistic data indicate that the accuracy potential of the hydrogen atomic beam exceeds that of either the cesium beam tube or the hydrogen maser, possibly by several orders of magnitude. In addition, with successful development, the hydrogen beam standard will have several other performance advantages over other devices, particularly exceptional stability and long continuous operating life. Experimental work with a new laboratory hydrogen beam device has recently resulted in the first resonance transition curves, measurements of relative state populations, beam intensities, etc. The most important aspects of both the hydrogen maser and the hydrogen beam work are covered.

Peters, H. E.↗

Biosensors for Real-Time Monitoring of Radiation-Induced Biologic Effects in Space

This proposal seeks to develop cellular biosensors based on dendritic polymers. Nanoscale polymer structures less than 20 nm in diameter will be used as the basis of the sensor/actuators. The structures will be designed to target into specific cells of an astronaut and be able to monitor health issues such as the exposure to radiation or infectious agents. Multiple components can be assembled on the polymers including target directors, analytical devices (such as molecular probes), magnetic particles and metals, and imaging agents. The design and assembly of these devices has been pioneered at the Center for Biologic Nanotechnology in the University of Michigan. These molecules would also be able to administer therapeutics in response to the needs of the astronaut, and act as actuators to remotely manipulate an astronaut as necessary to ensure their safety. The reporting will be accomplished either through fluorescence signal monitoring, with the use of multispectral analysis for signal interpretation, or through functional MRI. These nanosensors coupled to NEMS devices could facilitate the success and increase the safety of extended space flight.

Baker, James R., Jr.↗

Direct observation of the magnetic anisotropy of an Fe(II) spin crossover molecular thin film

Abstract In this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H 2 B(pz) 2 ) 2 (bipy)] (pz = pyrazol−1−yl, bipy = 2,2′−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10 −5 eV molecule −1 indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule −1 , respectively. Furthermore, the estimated g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations.

74 ATOMIC AND MOLECULAR PHYSICS↗

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant–polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1 H and 13 C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19 F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF–water complexes that serve as Brønsted acid sites, as revealed by 11 B ssNMR spectroscopy. These results indicate that the P4–dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

36 MATERIALS SCIENCE↗

Permethylation as a strategy for high–molecular–weight polysaccharide structure analysis by nuclear magnetic resonance—Case study of Xylella fastidiosa extracellular polysaccharide

Current practices for structural analysis of extremely large-molecular-weight polysaccharides via solution-state nuclear magnetic resonance (NMR) spectroscopy incorporate partial depolymerization protocols that enable polysaccharide solubilization in suitable solvents. Non-specific depolymerization techniques utilized for glycosidic bond cleavage, such as chemical degradation or ultrasonication, potentially generate structural fragments that can complicate complete and accurate characterization of polysaccharide structures. Utilization of appropriate enzymes for polysaccharide degradation, on the other hand, requires prior structural knowledge and optimal enzyme activity conditions that are not available to an analyst working with novel or unknown compounds. Herein, we describe an application of a permethylation strategy that allows the complete dissolution of intact polysaccharides for NMR structural characterization. This approach is utilized for NMR analysis of Xylella fastidiosa extracellular polysaccharide (EPS), which is essential for the virulence of the plant pathogen that affects multiple commercial crops and is responsible for multibillion dollar losses each year.

13C↗

Magnet-in-ferroelectric crystals exhibiting photomultiferroicity

Growing crystallographically incommensurate and dissimilar organic materials is fundamentally intriguing but challenging for the prominent cross-correlation phenomenon enabling unique magnetic, electronic, and optical functionalities. Here, we report the growth of molecular layered magnet-in-ferroelectric crystals, demonstrating photomanipulation of interfacial ferroic coupling. The heterocrystals exhibit striking photomagnetization and magnetoelectricity, resulting in photomultiferroic coupling and complete change of their color while inheriting ferroelectricity and magnetism from the parent phases. Under a light illumination, ferromagnetic resonance shifts of 910 Oe are observed in heterocrystals while showing a magnetization change of 0.015 emu/g. In addition, a noticeable magnetization change (8% of magnetization at a 1,000 Oe external field) in the vicinity of ferro-to-paraelectric transition is observed. The mechanistic electric-field-dependent studies suggest the photoinduced ferroelectric field effect responsible for the tailoring of photo-piezo-magnetism. The crystallographic analyses further evidence the lattice coupling of a magnet-in-ferroelectric heterocrystal system.

42 ENGINEERING↗

Spin-Correlated Radical Pairs as Magnetic Switches for Controlling Emissive Triplet States via Triplet–Triplet Energy Transfer

Magnetic fields offer a powerful means to control molecular emission, enabling quantum sensing and spin-level control of chemical reactions. Here, we demonstrate a strategy to magnetically control red to near-infrared phosphorescence via triplet–triplet energy transfer (TTET) from donor–chiral bridge–acceptor (D−χ–A) molecules that generate spin-correlated radical pairs (SCRPs) upon photoexcitation. These SCRPs yield non-emissive triplet excited states whose formation is sensitive to magnetic fields. Here, by transferring this energy to emissive Pt- and Pd-based π-extended porphyrins, we enable magnetic control over phosphorescence that would otherwise be unresponsive to weak magnetic fields (<1 T). This approach establishes a platform for quantifying magnetic field effects on silent triplet states while extending magnetically responsive emission into the near-infrared. Coupling SCRP-based molecular magnetic switches to long-wavelength emissive acceptors offers a new way for probing and modulating spin-dependent processes and triplet-state populations in molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Endurance Magneto-Electronic Switchable Molecular Electronic Crystal

Electrically switchable magnetic and electronic properties are promising for quantum sensing and information technology. Here, we report an electrically driven magnetic and electronic phase transition in molecular electronic crystal, potassium-7,7,8,8-tetracyanoquinodimethan, with the magneto-electric switching over 105 cycles at room temperature. Electron spin resonance study reveals the cooperative transition between spin and charge degrees of freedom. In addition, the mechanistic spectroscopy studies suggest the charges in an inhomogeneous conductor–insulator mixed state. Furthermore, the findings shown here suggest electrically controlled ordering in strongly correlated molecular crystal leads to dynamic magneto-electric switching, paving the way for developing molecular-based memory and switching devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Proton switching molecular magnetoelectricity

Abstract The convergence of proton conduction and multiferroics is generating a compelling opportunity to achieve strong magnetoelectric coupling and magneto-ionics, offering a versatile platform to realize molecular magnetoelectrics. Here we describe machine learning coupled with additive manufacturing to accelerate the design strategy for hydrogen-bonded multiferroic macromolecules accompanied by strong proton dependence of magnetic properties. The proton switching magnetoelectricity occurs in three-dimensional molecular heterogeneous solids. It consists of a molecular magnet network as proton reservoir to modulate ferroelectric polarization, while molecular ferroelectrics charging proton transfer to reversibly manipulate magnetism. The magnetoelectric coupling induces a reversible 29% magnetization control at ferroelectric phase transition with a broad thermal hysteresis width of 160 K (192 K to 352 K), while a room-temperature reversible magnetic modulation is realized at a low electric field stimulus of 1 kV cm −1 . The findings of electrostatic proton transfer provide a pathway of proton mediated magnetization control in hierarchical molecular multiferroics.

36 MATERIALS SCIENCE↗

Amplifying Magnetic Field Effects on Upconversion Emission via Molecular Qubit-Driven Triplet–Triplet Annihilation

Triplet-triplet annihilation (TTA) enables photon upconversion by combining two lower-energy triplet excitons to produce a higher-energy singlet exciton. This mechanism enhances light-harvesting efficiency for solar energy conversion and enables the use of lower-energy photons in bioimaging and photoredox catalysis applications. The magnetic modulation of such high-energy excitons presents an exciting opportunity to develop molecular quantum information technologies. While the spin dynamics of triplet exciton pairs are sensitive to external magnetic fields, the magnetic field effects (MFEs) associated with these pairs are generally limited by spin statistics to at most 10% at low fields (<1 Tesla), making them challenging to apply in technological advancements. In contrast, MFEs on spin-correlated radical pairs (SCRPs) can be significantly greater, surpassing those on triplet pairs. By using SCRPs-based molecular qubits as triplet sensitizers in the sensitized TTA scheme, we can magnetically modulate TTA and consequently, the delayed fluorescence of annihilators. In our current system, we have achieved more than 70% magnetic modulation of delayed fluorescence, effectively harnessing and even amplifying magnetic modulation within SCRPs to influence high-energy excitons. In conclusion, this work opens new opportunities for advancing spin-controlled chemical reactions and molecular quantum information technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Bonding Governs Complex Magnetism in MnPt 5 P

Subtle changes in chemical bonds may result in dramatic revolutions in magnetic properties in solid-state materials. MnPt 5 P, a derivative of the rare-earth-free ferromagnetic MnPt 5 As, was discovered and is presented in this work. Specifically, MnPt 5 P was synthesized, and its crystal structure and chemical composition were characterized by X-ray diffraction as well as energy-dispersive X-ray spectroscopy. Accordingly, MnPt 5 P crystallizes in the layered tetragonal structure with the space group P4/mmm (No. 123), in which the face-shared Mn@Pt 12 polyhedral layers are separated by P layers. In contrast to the ferromagnetism observed in MnPt 5 As, the magnetic properties measurements on MnPt 5 P show antiferromagnetic ordering occurs at ~188 K with a strong magnetic anisotropy in and out of the ab-plane. Moreover, a spin-flop transition appears when a high magnetic field is applied. An A-type antiferromagnetic structure was obtained from the analysis of powder neutron diffraction (PND) patterns collected at 150 and 9 K. Calculated electronic structures imply that hybridization of Mn-3d and Pt-5d orbitals is critical for both the structural stability and observed magnetic properties. Semiempirical molecular orbitals calculations on both MnPt 5 P and MnPt 5 As indicate that the lack of 4p character on the P atoms at the highest occupied molecular orbital (HOMO) in MnPt 5 P may cause the different magnetic behavior in MnPt 5 P compared to MnPt 5 As. The discovery of MnPt 5 P, along with our previously reported MnPt5As, parametrizes the end points of a tunable system to study the chemical bonding which tunes the magnetic ordering from ferromagnetism to antiferromagnetism with the strong spin–orbit coupling (SOC) effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic phase diagram of A 2 [FeCl 5 (H 2 O)] ( A = K, Rb, NH 4 )

Here, erythrosiderites with the formula A 2 FeX 5 ∙H 2 O, where A = Rb, K, and (NH 4 ) and X = Cl and Br are intriguing systems that possess various magnetic and electric phases, as well as multiferroic phases in which magnetism and ferroelectricity are coupled. In this report, we study the magnetic phase diagram of erythrosiderites as a function of superexchange interactions and magnetic anisotropies. To this end, we perform classical Monte Carlo simulations on magnetic Hamiltonians that contain five different superexchange interactions with single-ion anisotropies. Our phase diagram contains all magnetic ground states that have been experimentally observed in these materials. We argue that the ground states can be explained by varying the ratio of $\frac{J_4}{J_2}$. For $\frac{J_4}{J_2}$ > 0.95 a cycloidal spins structure is stabilized as observed in (NH 4 ) 2 FeCl 5 ∙H 2 O and otherwise a collinear spin structure is stabilized as observed in (K,Rb) 2 FeCl 5 ∙H 2 O. We also show that the difference in the single-ion anisotropy along a- and c- axes is essential to stabilize the intermediate state observed in (NH) 2 FeCl 5 ∙H 2 O.

36 MATERIALS SCIENCE↗