Spin-triplet State Research Articles

Field-Induced Tuning of the Pairing State in a Superconductor

A magnetic field tunes UTe${}_{2}$ between two superconducting pairing mechanisms, possibly driving a change from a spin-triplet state to a spin-singlet state. This enables explorations of how exotic spin-triplet superconductivity emerges.

Perovskite-Sensitized Upconversion under Operando Conditions

Perovskite-sensitized upconversion (UC) has resulted in near-infrared-to-visible UC at solar-relevant fluxes. However, the successful implementation of UC devices into operating solar cells will result in exposure to similar environmental stressors as for the commercial photovoltaics (PVs), mainly elevated temperatures, and continuous irradiation. In this article, we investigated the effects of these two stressors, heat and light, on the triplet generation process at the perovskite/rubrene interface. Following exposure to both stressors, local discrepancies across the upconversion device were discovered. The first region showed changes to the morphology, and no detectable upconverted emission was observed. Through the combination of optical microscopy and spectroscopy, crystallization of the organic semiconductor layer, degradation of dibenzotetraphenylperiflanthene, and concurrent degradation of the perovskite sensitizer were found. These effects culminate in a reduction in both triplet generation and triplet–triplet annihilation. In the second region, no changes to the morphology were present and visible UC emission was observed following exposure to both stressors. To probe the triplet sensitization process at elevated temperatures, transient absorption spectroscopy was performed. The presence of the excited spin-triplet state of rubrene at 60 °C highlighted successful triplet generation even at elevated temperatures. This work emphasizes the challenges and continued potential for the integration of perovskite-sensitized UC into commercial photovoltaic devices.

Experimental evidence for spin–triplet states in Titanium implanted AlN film: An electron spin resonance study

Spin carrying defects in wide-bandgap semiconductors are promising candidates for the development of quantum information and quantum sensing technology. Here we report experimental evidence for the formation of paramagnetic defects in AlN films, subjected to high-energy hydrogen and titanium ion implantation. X-ray diffraction and Raman spectroscopy show that ion species and implantation process could alter the amount of local strain in AlN films. Electron spin resonance spectroscopy reveals resonance peaks with g-value higher than the one of a free electron (2.0023) for both H-implanted and Ti-implanted AlN films. The origin of these peaks is identified and attributed to different types of point defects. For the Ti-implanted film, in addition to the central peak, a half-field resonance peak has been detected and assigned to spin–triplet (S=1). These results provide new insight into the electronic spin state of point defects in AlN, which opens up interesting perspectives for applications to quantum devices.

Ubiquitous spin freezing in the superconducting state of UTe2

In most superconductors electrons form Cooper pairs in a spin-singlet state mediated by either phonons or by long-range interactions such as spin fluctuations. The superconductor UTe2 is a rare material wherein electrons are believed to form pairs in a unique spin-triplet state with potential topological properties. While spin-triplet pairing may be mediated by ferromagnetic or antiferromagnetic fluctuations, experimentally, the magnetic properties of UTe2 are unclear. By way of muon spin rotation/relaxation (μSR) measurements on independently grown UTe2 single crystals we demonstrate the existence of magnetic clusters that gradually freeze into a disordered spin frozen state at low temperatures. Our findings suggest that inhomogeneous freezing of magnetic clusters is linked to the ubiquitous residual linear term in the temperature dependence of the specific heat (C) and the low-temperature upturn in C/T versus T. The omnipresent magnetic inhomogeneity has potential implications for experiments aimed at establishing the intrinsic low-temperature properties of UTe2.

Large-bias spectroscopy of Yu-Shiba-Rusinov states in a double quantum dot

We have performed tunnel transport spectroscopy on a quantum dot (QD) molecule proximitized by a superconducting contact. In such a system, the scattering between QD spins and Bogoliubov quasiparticles leads to the formation of Yu-Shiba-Rusinov (YSR) states within the superconducting gap. In this work, we investigate interactions appearing when one- and two-electron spin states in a double-QD energetically align with the superconducting gap edge. We find that the inter-dot spin-triplet state interacts considerably stronger with the superconductor than the corresponding singlet, pointing to stronger screening. By forming a ring molecule with a significant orbital contribution to the effective g-factor, we observe interactions of all four spin-orbital one-electron states with the superconductor under a weak magnetic field.

Hamiltonian simulation of quantum beats in radical pairs undergoing thermal relaxation on near-term quantum computers.

Quantum dynamics of the radical pair mechanism is a major driving force in quantum biology, materials science, and spin chemistry. The rich quantum physical underpinnings of the mechanism are determined by a coherent oscillation (quantum beats) between the singlet and triplet spin states and their interactions with the environment, which is challenging to experimentally explore and computationally simulate. In this work, we take advantage of quantum computers to simulate the Hamiltonian evolution and thermal relaxation of two radical pair systems undergoing the quantum beats phenomenon. We study radical pair systems with nontrivial hyperfine coupling interactions, namely, 9,10-octalin+/p-terphenyl-d14 (PTP)- and 2,3-dimethylbutane (DMB)+/p-terphenyl-d14 (PTP)- with one and two groups of magnetically equivalent nuclei, respectively. Thermal relaxation dynamics in these systems are simulated using three methods: Kraus channel representations, noise models on Qiskit Aer and the inherent qubit noise present on the near-term quantum hardware. By leveraging the inherent qubit noise, we are able to simulate the noisy quantum beats in the two radical pair systems better than with any classical approximation or quantum simulator. While classical simulations of paramagnetic relaxation grow errors and uncertainties as a function of time, near-term quantum computers can match the experimental data throughout its time evolution, showcasing their unique suitability and future promise in simulating open quantum systems in chemistry.

Dynamic-dependent selectivity in a bisphosphine iron spin crossover C-H insertion/π-coordination reaction.

Reaction pathway selectivity is generally controlled by competitive transition states. Organometallic reactions are complicated by the possibility that electronic spin state changes rather than transition states can control the relative rates of pathways, which can be modeled as minimum energy crossing points (MECPs). Here we show that in the reaction between bisphosphine Fe and ethylene involving spin state crossover (singlet and triplet spin states) that neither transition states nor MECPs model pathway selectivity consistent with experiment. Instead, single spin state and mixed spin state quasiclassical trajectories demonstrate nonstatistical intermediates and that C-H insertion versus π-coordination pathway selectivity is determined by the dynamic motion during reactive collisions. This example of dynamic-dependent product outcome provides a new selectivity model for organometallic reactions with spin crossover.

Triplet states in the reaction center of Photosystem II.

In oxygenic photosynthesis sunlight is harvested and funneled as excitation energy into the reaction center (RC) of Photosystem II (PSII), the site of primary charge separation that initiates the photosynthetic electron transfer chain. The chlorophyll ChlD1 pigment of the RC is the primary electron donor, forming a charge-separated radical pair with the vicinal pheophytin PheoD1 (ChlD1+PheoD1-). To avert charge recombination, the electron is further transferred to plastoquinone QA, whereas the hole relaxes to a central pair of chlorophylls (PD1PD2), subsequently driving water oxidation. Spin-triplet states can form within the RC when forward electron transfer is inhibited or back reactions are favored. This can lead to formation of singlet dioxygen, with potential deleterious effects. Here we investigate the nature and properties of triplet states within the PSII RC using a multiscale quantum-mechanics/molecular-mechanics (QM/MM) approach. The low-energy spectrum of excited singlet and triplet states, of both local and charge-transfer nature, is compared using range-separated time-dependent density functional theory (TD-DFT). We further compute electron paramagnetic resonance properties (zero-field splitting parameters and hyperfine coupling constants) of relaxed triplet states and compare them with available experimental data. Moreover, the electrostatic modulation of excited state energetics and redox properties of RC pigments by the semiquinone QA- is described. The results provide a detailed electronic-level understanding of triplet states within the PSII RC and form a refined basis for discussing primary and secondary electron transfer, charge recombination pathways, and possible photoprotection mechanisms in PSII.

Generating spin-triplet states at the bulk perovskite/organic interface for photon upconversion.

Perovskite-sensitized triplet-triplet annihilation (TTA) upconversion (UC) holds potential for practical applications of solid-state UC ranging from photovoltaics to sensing and imaging technologies. As the triplet sensitizer, the underlying perovskite properties heavily influence the generation of spin-triplet states once interfaced with the organic annihilator molecule, typically polyacene derivatives. Presently, most reported perovskite TTA-UC systems have utilized rubrene doped with ∼1% dibenzotetraphenylperiflanthene (RubDBP) as the annihilator/emitter species. However, practical applications require a larger apparent anti-Stokes than is currently achievable with this system due to the inherent 0.4 eV energy loss during triplet generation. In this minireview, we present the current understanding of the triplet sensitization process at the perovskite/organic semiconductor interface and introduce additional promising annihilators based on anthracene derivatives into the discussion of future directions in perovskite-sensitized TTA-UC.

Electron Correlation in the Iron(II) Porphyrin by Natural Orbital Functional Approximations.

The relative stability of the singlet, triplet, and quintet spin states of iron(II) porphyrin (FeP) represents a challenging problem for electronic structure methods. While it is currently accepted that the ground state is a triplet, multiconfigurational wave function-based methods predict a quintet, and density functional approximations vary between triplet and quintet states, leading to a prediction that highly depends on the features of the method employed. The recently proposed Global Natural Orbital Functional (GNOF) aims to provide a balanced treatment between static and dynamic correlation, and together with the previous Piris Natural Orbital Functionals (PNOFs), allowed us to explore the importance of each type of correlation in the stability order of the states of FeP with a method that conserves the spin of the system. It is noteworthy that GNOF correlates all electrons in all available orbitals for a given basis set; in the case of the FeP with a double-ζ basis set as used in this work, this means that GNOF can properly correlate 186 electrons in 465 orbitals, significantly increasing the sizes of systems amenable to multiconfigurational treatment. Results show that PNOF5, PNOF7s, and PNOF7 predict the quintet to have a lower energy than the triplet state; however, the addition of dynamic correlation via second-order Møller-Plesset corrections (NOF-MP2) turns the triplet state to be lower than the quintet state, a prediction also reproduced by GNOF that incorporates much more dynamic correlation than its predecessors.

Identification of histidine‐Ni (II) metal complex by Raman spectroscopy

AbstractMetal ions such as nickel have a strong binding affinity to amino acids and form metal complexes of different geometry. This complex formation is influenced by many factors among others the kind of reactants and their relative concentrations, pH, and its effect on the net charge of the amino acid molecule. In this work, the formation of the histidine‐nickel (II) complex in different conditions was examined by Raman spectroscopy. In addition to the experiments, density functional theory (DFT) calculations on histidine‐nickel complexes were performed in order to elucidate the complex formation mechanism and optimal geometry of the structures as well as to investigate their vibrational properties. The Raman measurements showed double peaks at 1272 and 1297 cm−1, and triple peaks at 1322, 1336, and 1355 cm−1 that belong to the metal complex. The geometry optimizations and total energy calculations of His‐Ni (II) complex revealed that the octahedral geometry and the triplet spin state of Ni ion is the energetically favorable structure. This metal complex is formed through the nitrogen atom of the imidazole side chain, the nitrogen atom of the terminal amino group, and the oxygen atom of the carboxyl group. Experiments with pH revealed that the alkaline pH favors while the change of the concentration of the metal ions does not affect the the His‐Ni (II) complex formation.

Anomalous electromagnetic response in the spin-triplet superconductor UTe2

The recently discovered heavy-fermion superconductor ${\mathrm{UTe}}_{2}$, as a promising candidate for an odd-parity superconductivity, exhibits anomalous magnetic-field reinforced superconductivity with a huge upper critical field of 35 T. However, the thermodynamic properties of this unconventional superconductivity still remain unclear. Herein we present the results of dc magnetization and heat capacity measurements in ${\mathrm{UTe}}_{2}$ to probe the magnetic response at low temperatures. The obtained isothermal magnetization in the superconducting state of ${\mathrm{UTe}}_{2}$ clearly demonstrates the anomalous magnetic flux pinning effect, which is most likely related to the peculiar electromagnetic response of the spin-triplet pairing state in the hard-magnetization axis (orthorhombic $b$ axis). The ac susceptibility measurements support the anomalous vortex states in ${\mathrm{UTe}}_{2}$. We also found evidence for the Lifshitz transition just above ${H}_{\mathrm{c}2}$ and the anomalous flux pinning anomalies for the easy-magnetization axis ($a$ axis).

Triplet Spin-State Capped Deltahedral Structures Rather than Singlet Spin-State Oblatocloso Structures as Energetically Favored Dimanganaborane Structures

Density functional studies show that the singlet spin-state flattened oblatocloso deltahedral structures found experimentally in the dimetallaboranes Cp*2Re2Bn-2Hn-2 (Cp* = Me5C5; n = 8-12) of the third row group 7 element rhenium are not favored for analogous dimetallaboranes Cp2Mn2Bn-2Hn-2 (n = 8-14) of its first row congener manganese. Instead, the energetically preferred structures for the dimanganaboranes are higher spin-state triplet and quintet spin-state structures. This appears to be related to the lower ligand field splittings in complexes of the first row transition-metal manganese relative to analogous complexes of the third row transition-metal rhenium. The lowest-energy Cp2Mn2Bn-2Hn-2 (n = 8-13) structures typically have a central MnBn-2 closo deltahedron with one face capped by the second CpMn unit. However, for the 14-vertex Cp2Mn2B12H12 system the lowest-energy structures consist of B12 icosahedra with faces capped by both CpMn units. The thermochemistry of cluster buildup reactions of the type Cp2Mn2Bn-2Hn-2 + BH → Cp2Mn2Bn-1Hn-1 suggests that the 11- and 13-vertex structures are likely to be favored products in reactions of cyclopentadienylmanganese derivatives with borane sources. The paramagnetism of the predicted triplet and quintet spin states for the lowest-energy dimanganaboranes Cp2Mn2Bn-2Hn-2 (n = 8-14) suggests possible applications in novel magnetic materials.

Spin-defect qubits in two-dimensional transition metal dichalcogenides operating at telecom wavelengths

Solid state quantum defects are promising candidates for scalable quantum information systems which can be seamlessly integrated with the conventional semiconductor electronic devices within the 3D monolithically integrated hybrid classical-quantum devices. Diamond nitrogen-vacancy (NV) center defects are the representative examples, but the controlled positioning of an NV center within bulk diamond is an outstanding challenge. Furthermore, quantum defect properties may not be easily tuned for bulk crystalline quantum defects. In comparison, 2D semiconductors, such as transition metal dichalcogenides (TMDs), are promising solid platform to host a quantum defect with tunable properties and a possibility of position control. Here, we computationally discover a promising defect family for spin qubit realization in 2D TMDs. The defects consist of transition metal atoms substituted at chalcogen sites with desirable spin-triplet ground state, zero-field splitting in the tens of GHz, and strong zero-phonon coupling to optical transitions in the highly desirable telecom band.

Josephson current via spin and orbital states of a tunable double quantum dot

Supercurrent transport is experimentally studied in a Josephson junction hosting a double quantum dot (DQD) with tunable symmetries. The QDs are parallel-coupled to two superconducting contacts and can be tuned between strong inter-dot hybridization and a ring geometry where hybridization is suppressed. In both cases, we observe supercurrents when the two interacting orbitals are either empty or filled with spins, or a combination. However, when each QD hosts an unpaired spin, the supercurrent depends on the spin ground state. It is strongly suppressed for the ring geometry with a spin-triplet ground state at zero external magnetic field. By increasing the QD hybridization, we find that a supercurrent appears when the ground state changes to spin-singlet. In general, supercurrents are suppressed in cases of spin doublet ground state, but an exception occurs at orbital degeneracy when the system hosts one additional spin, as opposed to three, pointing to a broken particle-hole symmetry.

Superconductivity from repulsive interactions on the kagome lattice

The discovery of superconductivity in layered vanadium-based kagome metals $A$V$_3$Sb$_5$ ($A$: K, Rb, Cs) has added a new family of materials to the growing class of possible unconventional superconductors. However, the nature of the superconducting pairing in these materials remains elusive. We present a microscopic theoretical study of the leading superconducting instabilities on the kagome lattice based on spin- and charge-fluctuation mediated Cooper pairing. The applied methodology includes effects of both on-site and nearest-neighbor repulsive Coulomb interactions. Near the upper van Hove filling -- relevant for the $A$V$_3$Sb$_5$ materials -- we find a rich phase diagram with several pairing symmetries being nearly degenerate. In particular, while a substantial fraction of the phase diagram is occupied by a spin-singlet order parameter transforming as a two-dimensional irreducible representation of the point group, several nodal spin-triplet pairing states remain competitive. We compute the band and interaction parameter-dependence of the hierarchy of the leading superconducting instabilities, and determine the detailed momentum dependence of the resulting preferred gap structures. Crucially, for moderate values of the interaction parameters, the individual pairing states depend strongly on momentum and exhibit multiple nodes on the Fermi surface. We discuss the properties of these superconducting gap structures in light of recent experimental developments of the $A$V$_3$Sb$_5$ materials.

Quantum-based Modeling of Protein-ligand Interaction: The Complex of RutA with Uracil and Molecular Oxygen.

Modern quantum-based methods are employed to model interaction of the flavin-dependent enzyme RutA with the uracil and oxygen molecules. This complex presents the structure of reactants for the chain of chemical reactions of monooxygenation in the enzyme active site, which is important in drug metabolism. In this case, application of quantum-based approaches is an essential issue, unlike conventional modeling of protein-ligand interaction with force fields using molecular mechanics and classical molecular dynamics methods. We focus on two difficult problems to characterize the structure of reactants in the RutA-FMN-O2 -uracil complex, where FMN stands for the flavin mononucleotide species. First, location of a small O2 molecule in the triplet spin state in the protein cavities is required. Second, positions of both ligands, O2 and uracil, must be specified in the active site with a comparable accuracy. We show that the methods of molecular dynamics with the interaction potentials of quantum mechanics/molecular mechanics theory (QM/MM MD) allow us to characterize this complex and, in addition, to surmise possible reaction mechanism of uracil oxygenation by RutA.

Emergence of Spinmerism for Molecular Spin-Qubits Generation.

Molecular platforms are regarded as promising candidates in the generation of units of information for quantum computing. Herein, a strategy combining spin-crossover metal ions and radical ligands is proposed from a model Hamiltonian first restricted to exchange interactions. Unusual spin states structures emerge from the linkage of a singlet/triplet commutable metal centre with two doublet-radical ligands. The ground state nature is modulated by charge transfers and can exhibit a mixture of triplet and singlet local metal spin states. Besides, the superposition reaches a maximum for , suggesting a necessary competition between the intramolecular and inter-metal-ligand and direct exchange interactions. The results promote spinmerism, an original manifestation of quantum entanglement between the spin states of a metal centre and radical ligands. The study provides insights into spin-coupled compounds and inspiration for the development of molecular spin-qubits.

Computational Insights into Electronic Excitations, Spin-Orbit Coupling Effects, and Spin Decoherence in Cr(IV)-Based Molecular Qubits.

The great success of point defects and dopants in semiconductors for quantum information processing has invigorated a search for molecules with analogous properties. Flexibility and tunability of desired properties in a large chemical space have great advantages over solid-state systems. The properties analogous to point defects were demonstrated in the Cr(IV)-based molecular family, Cr(IV)(aryl)4, where the electronic spin states were optically initialized, read out, and controlled. Despite this kick-start, there is still a large room for enhancing properties crucial for molecular qubits. Here, we provide computational insights into key properties of the Cr(IV)-based molecules aimed at assisting the chemical design of efficient molecular qubits. Using the multireference ab initio methods, we investigate the electronic states of Cr(IV)(aryl)4 molecules with slightly different ligands, showing that the zero-phonon line energies agree with the experiment and that the excited spin-triplet and spin-singlet states are highly sensitive to small chemical perturbations. By adding spin-orbit interaction, we find that the sign of the uniaxial zero-field splitting (ZFS) parameter is negative for all considered molecules and discuss optically induced spin initialization via non-radiative intersystem crossing. We quantify (super)hyperfine coupling to the 53Cr nuclear spin and to the 13C and 1H nuclear spins, and we discuss electron spin decoherence. We show that the splitting or broadening of the electronic spin sub-levels due to superhyperfine interaction with 1H nuclear spins decreases by an order of magnitude when the molecules have a substantial transverse ZFS parameter.

Aufbau principle and singlet‐triplet gap in spherical Hooke atoms

AbstractSinglet and triplet spin state energies for three‐dimensional Hooke atoms, that is, electrons in a quadratic confinement, with even number of electrons (2, 4, 6, 8, 10) is discussed using Full‐CI and CASSCF type wavefunctions with a variety of basis sets and considering perturbative corrections up to second order. The effect of the screening of the electron–electron interaction is also discussed by using a Yukawa‐type potential with different values of the Yukawa screening parameter (λee = 0.2, 0.4, 0.6, 0.8, 1.0). Our results show that the singlet state is the ground state for two and eight electron Hooke atoms, whereas the triplet is the ground spin state for 4‐, 6‐, and 10‐electron systems. This suggests the following Aufbau structure 1s < 1p < 1d with singlet ground spin states for systems in which the generation of the triplet implies an inter‐shell one‐electron promotion, and triplet ground states in cases when there is a partial filling of electrons of a given shell. It is also observed that the screening of electron–electron interactions has a sizable quantitative effect on the relative energies of both spin states, specially in the case of two‐ and eight‐electron systems, favoring the singlet state over the triplet. However, the screening of the electron–electron interaction does not provoke a change in the nature of the ground spin state of these systems. By analyzing the different components of the energy, we have gained a deeper understanding of the effects of the kinetic, confinement and electron–electron interaction components of the energy.