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Results for “spin crossover effect”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface Charge and Electrostatic Spin Crossover Effects in CoN 4 Electrocatalysts

Carbon materials doped with nitrogen and 3d transition metals have attracted a great deal of interest for catalyzing electrochemical reactions such as water splitting, oxygen reduction, and carbon dioxide reduction. Here, we employed density functional theory to study Co–N-doped carbon as electrocatalysts for the oxygen reduction and oxygen evolution reactions. Specifically, we investigated the interplay among adsorption energies, the spin state of the CoN 4 active center, and the applied potential. We found that adsorption energies strongly depend on both the applied potential and the spin state of the Co center. Furthermore, spin state transitions induced by the applied potential also play an important role in determining the adsorption energies. Here, this effect originates from a different potential of zero charge and capacitance of each spin state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Giant and Reversible Barocaloric Effect in Trinuclear Spin–Crossover Complex Fe 3 (bntrz) 6 (tcnset) 6

A giant barocaloric effect (BCE) in a molecular material Fe 3 (bntrz) 6 (tcnset) 6 (FBT) is reported, where bntrz = 4-(benzyl)-1,2,4-triazole and tcnset = 1,1,3,3-tetracyano-2-thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin-state switching between the state in which all three FeII centers are in the high-spin (S = 2) electronic configuration and the state in which all of them are in the low-spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X-ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin-transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg –1 K –1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Evidence of dynamical effects and critical field in a cobalt spin crossover complex

The [Co(SQ) 2 (4-CN-py) 2 ] complex exhibits dynamical effects over a wide range of temperature. Additionally, the orbital moment, determined by X-ray magnetic circular dichroism (XMCD) with decreasing applied magnetic field, indicates a nonzero critical field for net alignment of magnetic moments, an effect not seen with the spin moment of [Co(SQ) 2 (4-CN-py) 2 ].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Evidence of Cooperative Effects for the Fe(phen) 2 (NCS) 2 Spin Crossover Molecular Complex in Polyaniline Plus Iron Magnetite

The spin crossover complex Fe(phen) 2 (NCS) 2 and its composite, Fe(phen) 2 (NCS) 2 , combined with the conducting polymer polyaniline (PANI) plus varying concentrations of iron magnetite (Fe 3 O 4 ) nanoparticles were studied. A cooperative effect is evident from the hysteresis width in the plot of magnetic susceptibility multiplied by temperature versus temperature (χ m T versus T) for Fe(phen) 2 (NCS) 2 with PANI plus varying concentrations of Fe 3 O 4 nanoparticles. The hysteresis width in the composites vary no more than 2 K with respect to the pristine Fe(phen) 2 (NCS) 2 spin crossover crystallites despite the fact that there exists a high degree of miscibility of the Fe(phen) 2 (NCS) 2 spin crossover complex with the PANI. The Fe 3 O 4 nanoparticles in the Fe(phen) 2 (NCS) 2 plus PANI composite tend to agglomerate at higher concentrations regardless of the spin state of Fe(phen) 2 (NCS) 2 . Of note is that the Fe 3 O 4 nanoparticles are shown to be antiferromagnetically coupled with the Fe(phen) 2 (NCS) 2 when Fe(phen) 2 (NCS) 2 is in the high spin state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Equation of State and Spin Crossover of (Al, Fe)–Phase H

The transport of hydrogen into Earth's deep interior may have an impact on lower mantle dynamics as well as on the seismic signature of subducted material. Due to the stability of the hydrous phases δ-AlOOH (delta phase), MgSiO 2 (OH) 2 (phase H), and ε-FeOOH at high temperatures and pressures, their solid solutions may transport significant amounts of hydrogen as deep as the core-mantle boundary. Here we have constrained the equation of state, including the effects of a spin crossover in the Fe 3+ atoms, of (Al, Fe)-phase H: Al 0.84 Fe 3+ 0.07 Mg 0.02 Si 0.06 OOH, using powder X-ray diffraction measurements to 125 GPa, supported by synchrotron Mössbauer spectroscopy measurements on (Al, Fe)-phase H and δ-(Al, Fe)OOH. The changes in spin state of Fe 3+ in (Al, Fe)-phase H results in a significant decrease in bulk sound velocity and occurs over a different pressure range (48–62 GPa) compared with δ-(Al, Fe)OOH (32–40 GPa). Changes in axial compressibilities indicate a decrease in the compressibility of hydrogen bonds in (Al, Fe)-phase H near 30 GPa, which may be associated with hydrogen bond symmetrization. The formation of (Al, Fe)-phase H in subducted oceanic crust may contribute to scattering of seismic waves in the mid-lower mantle (~1,100–1,550 km). Accumulation of 1–4 wt.% (Al, Fe)-phase H could reproduce some of the seismic signatures of large, low seismic-velocity provinces. Our results suggest that changes in the electronic structure of phases in the (δ-AlOOH)-(MgSiO 2 (OH) 2 )-(ε-FeOOH) solid solution are sensitive to composition and that the presence of these phases in subducted oceanic crust could be seismically detectable throughout the lower mantle.

58 GEOSCIENCES↗
DOE OSTI2024

Electronic transport properties of spin-crossover polymer plus polyaniline composites with Fe 3 O 4 nanoparticles

Abstract Adding Fe 3 O 4 nanoparticles to composites of [Fe(Htrz) 2 (trz)](BF 4 ) spin-crossover polymer and polyaniline (PANI) drives a phase separation of both and restores the molecular structure and cooperative effects of the spin-crossover polymer without compromising the increased conductivity gained through the addition of PANI. We observe an increased on-off ratio for the DC conductivity owing to an enlarged off state resistivity and a 20 times larger AC conductivity of the on state compared with DC values. The Fe 3 O 4 nanoparticles, primarily confined to the [Fe(Htrz) 2 (trz)](BF 4 ) phase, are ferromagnetically coupled to the local moment of the spin-crossover molecule suggesting the existence of an exchange interaction between both components.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chiral effects at the metal center in Fe(III) spin crossover coordination salts

Evidence of chirality was observed at the Fe metal center in Fe(III) spin crossover coordination salts [Fe(qsal) 2 ][Ni(dmit) 2 ] and [Fe(qsal) 2 ](TCNQ) 2 from x-ray absorption (XAS) spectroscopy at the Fe 2p 3/2 core threshold. Based on the circularly polarized XAS data, the x-ray natural circular dichroism for [Fe(qsal) 2 ][Ni(dmit) 2 ] and [Fe(qsal) 2 ](TCNQ) 2 is far stronger than seen for [Fe(qsal) 2 ]Cl suggesting this natural circular dichroism signature is a ligand effect rather than a result of just a loss of octahedral symmetry on the Fe core. The larger the chiral effects in the Fe 2p core to bound XAS, the greater the perturbation of the Fe 2p 3/2 to 2p 1/2 spin–orbit splitting seen in the XAS spectra.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Effect of different crystallographic properties on the electrical conductivity of two polymorphs of a spin crossover complex

In this study, the structure and transport properties of two polymorphs, nanoparticles and nanorods, of the iron(II) triazole [Fe(Htrz) 2 (trz)](BF 4 ) spin crossover complex were compared. Conductive atomic force microscopy was used to map the electrical conductivity of individual nanoparticles and nanorods. The [Fe(Htrz) 2 (trz)](BF 4 ) nanorods showed significantly higher conductivity compared to nanoparticles. This difference in electrical conductivity is partially associated to the different Fe–N bond lengths in each of the polymorphs, with an inverse relationship between Fe–N bond length and conductivity. Transport measurements were done on the nanorods for both high spin (at 380 K) and low spin (at 320 K) states under dark and illuminated conditions. The conductance is highest for the low spin state under dark conditions. In illumination, the conductance change is much diminished.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Magnetic Field Perturbations to a Soft X-ray-Activated Fe (II) Molecular Spin State Transition

The X-ray-induced spin crossover transition of an Fe (II) molecular thin film in the presence and absence of a magnetic field has been investigated. The thermal activation energy barrier in the soft X-ray activation of the spin crossover transition for [Fe{H2B(pz)2}2(bipy)] molecular thin films is reduced in the presence of an applied magnetic field, as measured through X-ray absorption spectroscopy at various temperatures. The influence of a 1.8 T magnetic field is sufficient to cause deviations from the expected exponential spin state transition behavior which is measured in the field free case. We find that orbital moment diminishes with increasing temperature, relative to the spin moment in the vicinity of room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Pressure-induced spin crossover in a Fe 78 Si 9 B 13 metallic glass

The pressure effect on structures and properties of a Fe 78 Si 9 B 13 metallic glass was investigated by in situ high-pressure synchrotron Fe Kβ x-ray emission spectroscopy and x-ray diffraction, and electrical resistivity measurements up to ~51 GPa. The study reveals a reversible and continuous pressure-induced high- to low-spin crossover of Fe atoms in an amorphous structure. The changes of the local spin moment can be scaled to match its average atomic distance shrinkage very well during compression. The crossover of electronic spin states in the Fe 78 Si 9 B 13 metallic glass resembles that of typical crystalline Fe-bearing materials but without a sharp atomic volume collapse and an abrupt electrical resistivity jump. Furthermore, these findings could help guide applications of Fe-based metallic glasses as a soft ferromagnetic material at extreme conditions and also improve our understanding of magnetism and coupling of its changes with disordered atomic structures and other properties in metallic glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex

We investigate giant magnetoelectric coupling at a Mn 3+ spin crossover in [Mn III L]BPh 4 (L = (3,5-diBr-sal) 2 323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη 2 coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, in this work, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Spin crossover transition driven by pressure: Barocaloric applications

This article describes a mean-field theoretical model for Spin-Crossover (SCO) materials and explores its implications. It is based on a simple Hamiltonian that yields the high spin molar fraction as a function of temperature and pressure, as well as a temperature–pressure phase diagram for the SCO transition. In order to test the model, it was compared with the giant Barocaloric Effect (BCE) of the SCO material [FeL 2 ][B 4 ] 2 . Furthermore, we found that optical phonons are responsible for 92% of the total barocaloric entropy change. DFT calculations successively indicates that, as expected, the majority of this effect can be traced to low frequencies modes of vibration (400 cm -1 ), associated to the Fe coordination.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Toward understanding the dimensional crossover of canonical spin-glass thin films

Spin-glass thin films exhibit many features different from the bulk. The freezing temperatures of spin-glass films are suppressed for reduced thickness and follow the Kenning relation. The dynamics are altered near the vacuum interface. These phenomena are closely related to the lower critical dimension of spin glasses, the spin-glass correlation length, and the dimensional crossover from d = 3 to d = 2. In this article, we review the experimental facts and theoretical perspectives for spin-glass thin films. We focus on canonical spin-glass systems with the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction between magnetic impurities in a nonmagnetic host. Open questions to be addressed are emphasized.

interfacial effects↗
DOE OSTI2022

Perturbing the spin state and conduction of Fe (II) spin crossover complexes with TCNQ

In this study, we investigated modifications driven by 7,7,8,8-tetracyanoquinodimethane (TCNQ) to the spin state configuration of [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal and both spin state and electric conductivity of [Fe{H 2 B(pz) 2 } 2 (bipy)] and TCNQ mixtures. The Fe 2+ site in the [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal has a sizable orbital moment. During X-ray absorption measurements, the iron ion is partially excited to the high spin state and strong surface effects are indicated. Mixing TCNQ with the [Fe{H 2 B(pz) 2 } 2 (bipy)] spin crossover complex leads to a molecular combination with increased conductivity and drift carrier lifetimes. [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ, grown using dimethylformamide (DMF), are to great extent locked mainly in the low spin (LS) state across a broad temperature range and exhibit drift carrier lifetimes approaching 0.5 s. When deposited onto a ferroelectric polyvinylidenefluoride-hexafluoropropylene thin film substrate, [Fe{H 2 B(pz) 2 } 2 (bipy)], shows enhanced transistor carrier mobility, likely associated with the increasing cationic character of [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spin Hall effect of vorticity

Using mapping between topological defects in an easy-plane magnet and electrical charges, we study interplay between vorticity and spin currents. Here, we demonstrate that the flow of vorticity is accompanied by the transverse spin current generation; an effect which can be termed as the spin Hall effect of vorticity. We study this effect across the BKT transition and establish the role of dissipation and spin nonconservation in the crossover from spin superfluidity to diffusive spin transport. Our results pave the way for low power computing devices relying on vorticity and spin flows that can propagate over long distances.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗