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DOE OSTI2021

Local Distortions and Metal–Semiconductor–Metal Transition in Quasi-One-Dimensional Nanowire Compounds AV 3 Q 3 O δ (A = K, Rb, Cs and Q = Se, Te)

Metal cluster compounds have garnered renewed interest in the search for novel superconductors and topological semimetals owing to structural instabilities of metal-cluster geometries and broken symmetries. Here we synthesized needle-like crystals of the V-cluster-based quasi-one-dimensional (Q1D) materials AV 3 Q 3 O δ (A = K, Rb, Cs, Q= Se, Te) which can also be viewed as being composed of parallel nanowires. We examine how changes in their average and local structure control their electronic properties. All compounds crystallize in the TIFe 3 Te 3 -type structure (P6 3 /m space group) with infinite (V 3 )Q 3 ) - double-walled columnar chains separated by A + cations. Our single-crystal and synchrotron powder diffraction studies indicate oxygen atoms partially occupy the center site of the V 6 octahedral metal cluster cages in KV 3 Te 3 O 0.33 , RbV 3 Te 3 O 0.32 , and CsV 3 Te 3 O 0.35 , whereas KV 3 Se 3 is structurally oxygen-free. Our synchrotron X-ray pair distribution function (PDF) analyses indicate that the oxygen-free V 6 cluster octahedra in KV 3 Se 3 are highly distorted perpendicular to the chain direction even at room temperature, reducing the symmetry of the average structure from hexagonal P6 3 /m to monoclinic P2 1 /m. Our theoretical calculation supports this P2 1 /m distortion and suggests the structure further distorts to P2 1 or P2 1 /c at lower temperatures. In contrast, the oxygen-centered V-cluster in KV 3 Te 3 O 0.33 exhibits a V-3-triangle-trimerization along the chain direction. This feature is discernible from the local PDF and is consistent with lattice dynamical calculations based on density functional theory. Resistivity measurements indicate that KV 3 Se 3 exhibits metallic behavior, whereas a dramatic metal-semiconductor-metal transition emerges in KV 3 Te 3 O 6.33 , RbV 3 Te 3 O 0.32 , and CsV 3 Te 3 O 0.35 because of oxygen disorder and changes in local structure captured from our electronic structure analyses of the Fermi surface. Our investigation of the AV 3 Q 3 O 6 family demonstrates the importance of understanding local changes in structure driven by electronic instabilities, which can guide the search for new quantum materials in other low-dimensional cluster-compound materials.

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

Superconductivity in Y 4 RuGe 8 with a Vacancy-Ordered CeNiSi 2 -Type Superstructure

In this work, we report a new compound, Y 4 RuGe 8 , with a transition metal vacancy-ordered CeNiSi 2 -type superstructure, which has a superconducting transition at 1.3 K. Y 4 RuGe 8 crystals were grown by indium flux at relatively low temperatures (below 1273 K), which makes it possible to stabilize such a vacancy-ordered phase. The crystal structure of Y 4 RuGe 8 was solved by single-crystal X-ray diffraction and confirmed by transmission electron microscopy. The as-grown Y 4 RuGe 8 crystals are always twinned, crystallizing in the space group $P\bar{1}$(no. 2) with the lattice parameters a = 5.7680(1) Å, b = 8.2042(2) Å, c = 11.5093(3) Å, α = 79.696(1)degrees, β = 88.491(1)degrees, and γ = 79.637(2)degrees; this structure is a superstructure deriving from the higher symmetry CeNiSi 2 -type structure (Cmcm, no. 63) due to the ordering of Ru vacancies. The ordering of Ru sites breaks slightly distorted Ge planes in the CeNiSi 2 prototype into infinite cis-trans Ge chains in Y 4 RuGe 8 . The presence of bulk superconductivity in Y 4 RuGe 8 is well supported by zero resistance and a jump in specific heat at the critical transition temperature. The Sommerfeld coefficient (19 mJ K -2 mol -1 ) of the specific heat is greater than that (11 mJ K -2 mol -1 ) estimated using the bare density of states (4.7 states/eV/f.u.) from first-principles calculations. The ab initio calculations indicate that 4d electrons of both Y and Ru and 4p electrons of Ge are the main contributors to the total density of states at the Fermi level in Y 4 RuGe 8 .

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

Antiferromagnetic Order and Linear Magnetoresistance in Fe-Substituted Shandite Co 3 In 2 S 2

Co 3 In 2 S 2 is a shandite phase closely related to the ferromagnetic Weyl semimetal Co 3 Sn 2 S 2 and contains Co atoms on an ideal kagome net. Elemental substitutions in Co 3 Sn 2 S 2 have been shown to invariably suppress its magnetism, and it remains a rare example of a shandite phase with magnetic order. Here, we report a new magnetic shandite compound discovered by substituting Fe into Co 3 In 2 S 2 . Single crystals of (Co 1–x Fe x ) 3 In 2 S 2 were grown, and neutron diffraction, ac and dc magnetization, and heat capacity measurements reveal long-range antiferromagnetic order with an interesting noncollinear structure and transition temperatures from 11 to 17 K. Partially substituting Fe for Co was inspired by calculated electronic structures, which suggest that Co 3 In 2 S 2 is near a magnetic instability and shows a peak in the density of states that can be approached by hole doping. While the focus of the present work is primarily on magnetism, there is a nodal ring below the Fermi energy in Co 3 In 2 S 2 that may also provide interest from a topological perspective. Potentially related to this, we find large, linear, nonsaturating magnetoresistance in this compound. Furthermore, this work expands the scope of magnetic topological materials among shandites and motivates similar chemical manipulation studies to reveal hidden magnetic instabilities in this important family and other topological systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species

Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe 9.4(2) S 10 ][Fe(en) 3 ] 0.6(1) ·en 0.9 ( 3 ). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57 Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe 8 S 10 ][Fe(en) 3 ] 1 ·en 0.5 and tetragonal FeS. The new compound has flat Fe 9.4 S 10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 , the interlayer space is occupied by [Fe(en) 3 ] 2+ complexes and neutral ethylenediamine molecules in a ~2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (~6%) of iron vacancies at the Fe-S layer in [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Here, our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure–property relationships.

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

Probing of the Noninnocent Role of P in Transition-Metal Phosphide Hydrogen Evolution Reaction Electrocatalysts via Replacement with Electropositive Si

Transition-metal phosphides (TMP) have been identified as promising electrocatalysts for the hydrogen evolution reaction (HER). Despite recent computational investigations identifying P sites as being crucial for hydrogen adsorption, the main mode of optimization for TMPs has been focused on changing the metal sites. Here, to experimentally verify computational hypotheses and provide a route for HER electrocatalyst optimization via ternary compounds, we performed systematic experimental studies of structurally related NiSi 1–x P x phases, namely, Ni 2 SiP, Ni 5 Si 2 P 3 , Ni 3 SiP 2 , and Ni 7 Si 2 P 5 , which are ordered derivatives of the NiSi structure (Pnma, oP-8, MnP structure type). We found that P played a significant role in modulating HER activity in an acidic electrolyte because the incorporation of P in NiSi reduced the overpotential at current density j = 10 mA/cm 2 from η 10 = 529 mV (NiSi) to η 10 = 97 mV (Ni 2 SiP). Ni 2 SiP outperformed the current state-of-the-art Ni5P4 electrocatalyst prepared and studied in identical conditions both in terms of activity and stability, which is attributed to the presence of covalent Ni–Si bonding in the structure. Within the family of ternary Ni–Si–P compounds, electrocatalytic activity correlates with the number of Ni-3d states at the Fermi energy.

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

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V 2 O 5 Double Layers

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 –O 2p-hybridized mid-gap states mediated by second-order Jahn–Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V–V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V–V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

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

Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi 3 Bi 4 (Ln: La···Gd 3+ , Eu 2+ , Yb 2+ )

Here, we present a family of titanium-based kagome metals of the form LnTi 3 Bi 4 (Ln: La···Gd 3+ , Eu 2+ , Yb 2+ ). Four previously unreported compounds are presented: YbTi 3 Bi 4 , GdTi 3 Bi 4 , NdTi 3 Bi 4 , and PrTi 3 Bi 4 . Single-crystal growth methods are provided alongside detailed magnetic and thermodynamic measurements across the entire series. The LnTi 3 Bi 4 family of compounds are orthorhombic (Fmmm), layered compounds that exhibit slightly distorted titanium-based kagome nets interwoven with zigzag lanthanide-based (Ln) chains. Crystals are easily exfoliated parallel to the kagome sheets, and angular resolved photoemission (ARPES) measurements highlight the intricacy of the electronic structure in these compounds. Density functional theory (DFT) and ARPES studies find Dirac points near the Fermi level, consistent with the kagome-derived band structure. The magnetic properties and the associated anisotropy emerge from the quasi-1D zigzag chains of Ln and impart a wide array of magnetic ground states ranging from anisotropic ferromagnetism to complex antiferromagnetism with a cascade of metamagnetic transitions. In conclusion, the combination of the kagome-based electronic structure and highly anisotropic Ln-based magnetism on an exfoliatable platform cements the LnTi 3 Bi 4 family as an interesting addition to the ever-expanding suite of kagome metals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe 2 P Polymorphs

Iron phosphide (Fe 2 P) crystallizes in its own hexagonal crystal structure type (h-Fe 2 P). As found in meteorites, orthorhombic polymorph (o-Fe 2 P) was originally reported as a high-temperature and high-pressure phase. Recently, o-Fe 2 P was described as being stable at ambient pressure, yet no synthetic methods were developed for single-crystal growth or single-phase bulk powder synthesis. Here, we report a successful method for growing o-Fe 2 P single crystals and synthesizing phase-pure polycrystalline samples using tin-flux. In situ powder X-ray diffraction studies showed that the phase transition from o-Fe 2 P to h-Fe 2 P occurs at about 873 K, and below that temperature, the formation of the o-Fe 2 P phase is favored thermodynamically rather than kinetically. Systematic comparison of transport, magnetic, and electrocatalytic properties of both h-Fe 2 P and o-Fe 2 P phases showed a substantial impact of the crystal structure on properties. The orthorhombic structural distortion resulted in considerable changes in magnetic properties, with the o-Fe 2 P phase exhibiting a 60% lower Fe magnetic moment and a substantially higher ferromagnetic Curie temperature than h-Fe 2 P. Further, electrochemical measurements toward the hydrogen evolution reaction in acidic media showed that the o-Fe 2 P phase requires an 80 mV lower overpotential than the h-Fe 2 P phase to generate a current density of -10 mA/cm 2 , and their electronic structures suggest that the higher density of states at the Fermi energy is the origin of superior catalytic activity in o-Fe 2 P.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Tuning Thermal Stability through Dopant Size in Chemically Doped DPP–Thiophene Polymers

Molecular doping of conjugated polymers (CPs) is a key strategy for improving the performance of organic electronics devices, particularly thermoelectrics. Doped donor–acceptor (D–A) conjugated polymers, characterized by a tunable energy gap between the Fermi level and the transport band, show great promise in achieving high electrical conductivity (σ) while preserving a favorable Seebeck coefficient (S). Despite the promising performance enhancement of chemically doped D–A polymers, their thermal stability remains largely underexplored, a crucial consideration for the long-term operation of organic thermoelectric devices. In this study, we investigated the dopant size-dependent thermal stability of a diketopyrrolopyrrole-thiophene (DPP-T) D–A copolymer, utilizing two p-dopants: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) and Mo(tfd-CO 2 Me) 3 . Temperature-dependent UV–vis–NIR spectroscopy revealed that DPP-T/F 4 TCNQ is more prone to dedoping under a high temperature thermal stress than DPP-T/Mo(tfd-CO 2 Me) 3 . Although the F 4 TCNQ doped polymer shows higher initial in-plane conductivity than its Mo(tfd-CO 2 Me) 3 counterpart, it undergoes a conductivity loss of more than an order of magnitude after annealing at 120 °C for 30 min. In contrast, the in-plane conductivity of DPP-T/Mo(tfd-CO 2 Me) 3 remains stable under the same thermal conditions. Thermogravimetric analysis ruled out dopant sublimation as a primary contributor to dedoping, leading us to attribute the conductivity loss in F 4 TCNQ-doped DPP-T to dopant phase separation and migration. This observation was further confirmed by X-ray scattering studies and nanoscale infrared microscopy and spectroscopy studies. This work could provide further insights into the thermal stability of doped conjugated polymers and suggests that incorporating bulkier dopants is an effective strategy to enhance the thermal robustness of doped DPP-type systems.

Conjugated polymers↗
DOE OSTI2026

Mo 4 FeGa 17.25– x Ge x : Complementary Point Substitutions, Buffering Frameworks, and Merging of the 18-n and Octet Bonding Schemes

We present the discovery of Mo 4 FeGa 17.25–x Ge x (x ∼ 2.1(4), based on determination of Ge content), a complex gallide featuring a variety of point substitution phenomena. Its crystal structure is derived from the Ti 2 Ni type, in which a diamond network of face-sharing octahedra is interpenetrated by a second diamond network of vertex-sharing stella quadrangula. However, while in the ideal Ti 2 Ni type these two frameworks run uninterrupted through the crystal, Mo 4 FeGa 17.25–x Ge x shows three variations. First, the inner tetrahedron of every other stella quadrangula is replaced with a main group atom, creating tetrahedra reminiscent of the Zintl phase NaTl. Next, a selection of Ga 6 octahedra are filled with Fe atoms, in a manner analogous to the stuffed AuCu 3 -type phases. Finally, the refined crystal structure shows that in each unit cell a single Ga2 atom in the octahedral network is substituted with a dumbbell of Ga/Ge atoms. Electronic structure calculations on ordered models of Mo 4 FeGa 17.25–x Ge x reveal a narrow band near the Fermi energy, which is explained in terms of the 18-n and octet bonding schemes using reversed approximation Molecular Orbital analysis. A DFT-chemical pressure analysis connects the tetrahedron/atom and atom/dumbbell substitutions to the relief of atomic packing tensions and highlights soft atomic motions within the octahedral framework and driving forces for atom/dumbbell substitution. The combination of soft vibrational modes, disorder, and a narrow band gap could make this phase of interest for potential thermoelectric properties.

Chemical structure↗
DOE OSTI2020

Direct Evidence of Charge Transfer upon Anion Intercalation in Graphite Cathodes through New Electronic States: An Experimental and Theoretical Study of Hexafluorophosphate

Graphite intercalation compounds continue to be central to technologies for electrochemical energy storage from anodes in established Li-ion batteries to cathodes in beyond Li-ion concepts paired with multivalent anodes. When used as a cathode, graphite intercalates a variety of anions with PF 6 - being among the most common. Paired with Li intercalation at the anode, the corresponding dual carbon battery yields high energy and power densities. Given the available choice of anions as intercalants, it is important to elucidate how the graphite structure accommodates them in order to tailor the molecular species to maximize charge and reversibility. However, the changes in electronic structure of the host graphite lattice upon anion intercalation are poorly understood compared to cations, which represent a fundamentally different reaction. Herein, PF 6 -intercalated graphite has been studied using techniques sensitive to electronic structure, namely, X-ray Raman spectroscopy (XRS), X-ray absorption near-edge spectroscopy (XANES), and X-ray emission spectroscopy (XES). Complementary full-potential, all-electron density functional theory calculations yielded excellent agreement with the spectra, thus providing insight into charge compensation in the graphite lattice. In particular, a pre-$π^*$ feature emerged in XRS/XANES, which is direct evidence of the removal of charge from the host lattice to compensate the intercalated anions, leading to an overall lowering of the Fermi energy level. This is expected to be characteristic of many intercalants in anion-intercalated graphite. The unambiguous identification of the origin of the pre-$π^*$ spectral feature, which is frequently seen in graphitic systems, is of broad interest to the spectroscopy of graphitic systems beyond the practical implications of anion-induced changes in the electronic properties for real devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Li x (C 5 H 5 N) y Fe 2– z Se 2 : A Defect-Resilient Expanded-Lattice High-Temperature Superconductor

Two-dimensional iron chalcogenide intercalates display a remarkable correlation of the interlayer spacing with enhancement of the superconducting critical temperature (T c ). In this work, synchrotron X-ray absorption (XAS; at the Fe and Se K-edges) and emission (XES; at the Fe Κβ) spectroscopies allow one to discuss how the important rise of T c (~44 K) in the molecule-intercalated Li x (C 5 H 5 N) y Fe 2-z Se 2 relates to the electronic and local structural changes felt by the inorganic host upon doping (x). XES shows that widely separated layers of edge-sharing FeSe 4 tetrahedra carry low-spin moieties, with a local Fe magnetic moment slightly reduced compared to the parent β-Fe 2-z Se 2 . Pre-edge XAS expresses the progressively reduced mixing of metal 3d-4p states upon lithiation. Doping-mediated local lattice modifications, probed by conventional T c optimization measures (cf. the anion height and FeSe 4 tetrahedra regularity), become less relevant when layers are spaced far away. On the basis of extended X-ray absorption fine structure, such distortions are compensated by a softer Fe network that relates to Fe-site vacancies, alleviating electron-lattice correlations and superconductivity. Density functional theory (DFT) guided modification of the isolated Fe 2-z Se 2 (z, vacant sites) planes, resembling the host layers, identify that Fe-site deficiency occurs at low energy cost, giving rise to stretched Fe sheets, in accordance with experiments. Here, the robust high-T c in Li x (C 5 H 5 N) y Fe 2-z Se 2 , arises from the interplay of electron-donating spacers and the iron selenide layer's tolerance to defect chemistry, a tool to favorably tune its Fermi surface properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

IrGe 4 : A Predicted Weyl-Metal with a Chiral Crystal Structure

Polycrystalline IrGe4 was synthesized by annealing elements at 800 °C for 240 h, and the composition was confirmed by energy-dispersive X-ray spectroscopy. IrGe 4 adopts a chiral crystal structure (space group P3 1 21) instead of a polar crystal structure (P3 1 ), which was corroborated by the convergent-beam electron diffraction and Rietveld refinements using synchrotron powder X-ray diffraction data. The crystal structure features layers of IrGe 8 polyhedra along the b axis, and the layers are connected by edge- and corner-sharing. Each layer consists of corner-shared [Ir 3 Ge 20 ] trimers, which are formed by three IrGe 8 polyhedra connected by edge-sharing. Temperature-dependent resistivity indicates metallic behavior. The magnetoresistance increases with increasing applied magnetic field, and the nonsaturating magnetoresistance reaches 11.5% at 9 T and 10 K. The Hall resistivity suggests that holes are the majority carrier type, with a carrier concentration of 4.02 × 10 21 cm –3 at 300 K. In conclusion, electronic band structures calculated by density functional theory reveal a Weyl point with a chiral charge of +3 above the Fermi level.

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

Incommensurate Spiral Spin Order in CaMn 2 Bi 2 Observed via High-Pressure Neutron Diffraction

Here, high-pressure neutron diffraction is employed to investigate the magnetic behavior of CaMn 2 Bi 2 in extreme conditions. In contrast to antiferromagnetic ordering on Mn atoms reported at ambient pressure, our results reveal that at high pressure, incommensurate spiral spin order emerges due to the interplay between magnetism on the Mn atoms and strong spin–orbit coupling on the Bi atoms: sinusoidal spin order is observed at pressures as high as 7.4 GPa. First-principles calculations with a noncollinear spin orientation demonstrate band crossing behavior near the Fermi level as a result of strong hybridization between the d orbitals of Mn and the p orbitals of Bi atoms. Competing antiferromagnetic order is observed at different temperatures in the partially frustrated lattice. Theoretical models have been developed to investigate spin dynamics. This research provides a unique toolbox for conducting experimental and theoretical magnetic and spin dynamics studies of magnetic quantum materials via high-pressure neutron diffraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Predicting Quantum Criticality in Single-Crystalline Ce 2 Ru 3 Ge 5

Strongly correlated f-electron systems are known to host exotic quantum states, such as quantum criticality, complex order parameters, and unconventional superconductivity. However, the appearance of these exotic states is difficult to predict, making the study of quantum critical behavior challenging, especially in ferromagnetic materials. Herein, we report a structure–property map for Ce 2 M 3 X 5 (M = transition metal; X = main group element) that aids in the targeted design of materials likely to exhibit quantum criticality. Guided by this map, we report on the synthesis of single-crystalline Ce 2 Ru 3 Ge 5 and provide, for the first time, magnetic susceptibility, heat capacity, resistivity, and magnetoresistance measurements on single crystals. Here, we observe a weak ferromagnetic-like response at 7.5 K, which is contrasted with the bulk ferromagnetic ordering that appears in polycrystalline samples. Non-Fermi liquid behavior is seen in the temperature dependent electrical resistivity and heat capacity of the single crystals, suggesting proximity to a ferromagnetic quantum critical point without chemical or physical pressure. Given the contrast with previous reports of polycrystals, these results lead us to propose that single crystalline Ce 2 Ru 3 Ge 5 is intrinsically tuned into the vicinity of a ferromagnetic quantum critical point.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nature of Hyperfine Interactions in TbPc 2 Single-Molecule Magnets: Multiconfigurational Ab Initio Study

Lanthanide-based single-ion magnetic molecules can have large magnetic hyperfine interactions as well as large magnetic anisotropy. Recent experimental studies reported tunability of these properties by changes of chemical environments or by application of external stimuli for device applications. In order to provide insight onto the origin and mechanism of such tunability, here we investigate the magnetic hyperfine and nuclear quadrupole interactions for a 159 Tb nucleus in TbPc 2 (Pc = phthalocyanine) single-molecule magnets using multiconfigurational ab initio methods including spin–orbit interaction. Since the electronic ground and first-excited (quasi)doublets are well separated in energy, the microscopic Hamiltonian can be mapped onto an effective Hamiltonian with an electronic pseudospin S = 1/2. From the ab initio calculated parameters, we find that the magnetic hyperfine coupling is dominated by the interaction of the Tb nuclear spin with electronic orbital angular momentum. The asymmetric 4f-like electronic charge distribution leads to a strong nuclear quadrupole interaction with significant transverse terms for the molecule with low symmetry. The ab initio calculated electronic–nuclear spectrum including the magnetic hyperfine and quadrupole interactions is in excellent agreement with the experiment. We further find that the transverse quadrupole interactions significantly influence the avoided level crossings in magnetization dynamics and that the molecular distortions affect mostly the Fermi contact terms as well as the transverse quadrupole interactions. Synopsis Hyperfine interactions for 159 Tb nucleus in TbPc 2 single-molecule magnets are investigated from first-principles using multiconfigurational calculations. Strong nuclear quadrupole and magnetic hyperfine coupling are found, with the latter being dominated by the paramagnetic spin-orbital mechanism. Furthermore, we construct an ab initio pseudospin Hamiltonian and obtain the electronic-nuclear spectrum that is in excellent agreement with experiment. The Zeeman diagram is calculated, and the magnetization dynamics is discussed. The effects of molecular distortions are researched.

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

Adaptive Variational Quantum Computing Approaches for Green’s Functions and Nonlinear Susceptibilities

Here, we present and benchmark quantum computing approaches for calculating real-time single-particle Green’s functions and nonlinear susceptibilities of Hamiltonian systems. The approaches leverage adaptive variational quantum algorithms for state preparation and propagation. Using automatically generated compact circuits, the dynamical evolution is performed over sufficiently long times to achieve adequate frequency resolution of the response functions. We showcase accurate Green’s function calculations using a statevector simulator on classical hardware for Fermi-Hubbard chains of 4 and 6 sites, with maximal ansatz circuit depths of 65 and 424 layers, respectively, and for the molecule LiH with a maximal ansatz circuit depth of 81 layers. Additionally, we consider an antiferromagnetic quantum spin-1 model that incorporates the Dzyaloshinskii-Moriya interaction to illustrate calculations of the third-order nonlinear susceptibilities, which can be measured in two-dimensional coherent spectroscopy experiments. These results demonstrate that real-time approaches using adaptive parametrized circuits to evaluate linear and nonlinear response functions can be feasible with near-term quantum processors.

97 MATHEMATICS AND COMPUTING↗