An official website of the United States government
Abstract The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2−anion, is reported in the (NEt4)2[UF6]⋅2 H2O salt (1). The weak magnetic response of1results from both UIVspin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.
more »
« less
This content will become publicly available on June 30, 2026
Magnetically Driven Quantum Phase Transition in a Low-Dimensional Pyrazine-Bridged Cu 2+ Chain Magnet
The magnetic properties and phase diagrams of S = 1/2 quasi-one-dimensional Heisenberg antiferromagnets are well established with copper-containing coordination polymers as the platform of choice due to their low energy scales and ease of chemical substitution. The inability to uncover orbitally resolved components of the magnetization has, however, been a longstanding barrier to greater understanding of high field spin state transitions. In this work, we combine pulsed field magnetization, optical spectroscopy, and magnetic circular dichroism with complementary electronic structure calculations to unravel orbital-specific contributions to the magnetism in the linear chain quantum magnet [CuL2(H2O)2(pyz)](ClO4)2 [L = 5-methyl-2-pyridone; pyz = pyrazine]. In addition to revealing a spin flop and field-driven transition to the fully saturated spin state, we untangle the green → teal color change across the 185 K structural phase transition and employ what we learn about the different Cu2+ → pyrazine charge transfer excitations to decompose the magnetic circular dichroism. Analysis reveals that both eg-derived Cu2+ 3d orbitals play a role in the field-driven transition to the fully saturated state, not just those formally hosting unpaired electrons. We attribute the surprisingly strong dichroic signature at room temperature to the presence of uncorrelated spin.
more »
« less
- Award ID(s):
- 2342425
- PAR ID:
- 10651957
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 64
- Issue:
- 25
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 12518 to 12526
- Subject(s) / Keyword(s):
- quantum magnets, orbital decomposition of magnetism, high magnetic field properties
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Neutron powder diffraction (NPD) and x-ray magnetic circular dichroism (XMCD) spectroscopy are employed to investigate the magnetism and spin structure in single-phase B20 Co1.043Si0.957. The magnetic contributions to the NPD data measured in zero fields are consistent with the helical order among the allowed spin structures derived from group theory. The magnitude of the magnetic moment is (0.3 ± 0.1) μB/Co according to NPD, while the surface magnetization probed by XMCD at 3 kOe is (0.18–0.31) μB/Co. Both values are substantially larger than the bulk magnetization of 0.11 μB/Co determined from magnetometry at 70 kOe and 2 K. These experimental data indicate the formation of a helical spin phase and the associated conical states in high magnetic fields.more » « less
-
Abstract Owing to their overall low energy scales, flexible molecular architectures, and ease of chemical substitution, molecule-based multiferroics are extraordinarily responsive to external stimuli and exhibit remarkably rich phase diagrams. Even so, the stability and microscopic properties of various magnetic states in close proximity to quantum critical points are highly under-explored in these materials. Inspired by these opportunities, we combined pulsed-field magnetization, first-principles calculations, and numerical simulations to reveal the magnetic field–temperature (B–T) phase diagram of multiferroic (NH4)2FeCl5⋅H2O. In this system, a network of intermolecular hydrogen and halogen bonds creates a competing set of exchange interactions that generates additional structure in the phase diagram—both in the vicinity of the spin flop and near the 30 T transition to the fully saturated state. Consequently, the phase diagrams of (NH4)2FeCl5⋅H2O and its deuterated analog are much more complex than those of other molecule-based multiferroics. The entire series of coupled electric and magnetic transitions can be accessed with a powered magnet, opening the door to exploration and control of properties in this and related materials.more » « less
-
Abstract Magnetic high entropy alloys (HEAs) consisting of 3dtransition metals offer an exciting platform to explore novel magnetic phases as they often house competing exchange interactions in combination with random site disorders. In this work, a sensitive and tunable magnetic order is demonstrated in sputtered single‐layer FeCoNiMnAlxfilms, as a function of non‐magnetic Al addition, along with an unexpected exchange bias effect. Thin films of 50 nm FeCoNiMn exhibit a face‐centered‐cubic (fcc) phase, reentrant spin glass (SG) transition near 100 K, and a large exchange bias of over 500 Oe after field‐cooling to 5 K. The exchange bias is increased to 930 Oe through a small addition of 5 at.% Al. Further Al addition to 12 at.% results in a body‐centered‐cubic (bcc) phase, coinciding with a large increase in the saturation magnetization, decrease of exchange bias to 50 Oe, and suppression of SG behavior. The change in magnetic order across the Al‐induced structural transformation is mediated by the switching of Mn ground state from AF to FM, which is supported by first‐principles calculations and experimentally confirmed via X‐ray magnetic circular dichroism. These results open up new HEA strategies for explorations of novel magnetic phases.more » « less
-
The rise of quantum information science has spurred chemists to prepare new molecules that serve as useful building blocks in quantum technologies of the future. Implementation of molecular spin-based qubits requires new methods to induce high spin polarization of samples. Herein, we report design criteria to develop axially symmetric spin-1/2 molecules amenable to optically induced magnetization (OIM), a technique using circularly polarized (CP) excitation to deliver spin polarization. We apply these criteria to develop a series of tungsten(V) chalcogenide complexes that are demonstrated to have large spin-sensitive responses to CP light using magnetic circular dichroism (MCD) that could allow up to ∼20% spin polarization through OIM. Pulsed electron paramagnetic resonance (EPR) spectra reveal these systems have improved relaxation times over molecules like K2IrCl6, a species recently investigated by OIM, and field-swept electron spin−echo (FS-ESE) experiments show they have a remarkable lack of anisotropy in their phase-memory Tm times. The design criteria are general and point toward future ways to improve OIMinitializable qubits.more » « less
