Polarized Ground State Research Articles

Luminescent Organic Triplet Diradicals as Optically Addressable Molecular Qubits.

Optical-spin interfaces that enable the photoinitialization, coherent microwave manipulation, and optical read-out of ground state spins have been studied extensively in solid-state defects such as diamond nitrogen vacancy (NV) centers and are promising for quantum information science applications. Molecular quantum bits (qubits) offer many advantages over solid-state spin centers through synthetic control of their optical and spin properties and their scalability into well-defined multiqubit arrays. In this work, we report an optical-spin interface in an organic molecular qubit consisting of two luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals connected via the meta-positions of a phenyl linker. The triplet ground state of this system can be photoinitialized in its |T0⟩ state by shelving triplet populations as singlets through spin-selective excited-state intersystem crossing with 80% selectivity from |T+⟩ and |T-⟩. The fluorescence intensity in the triplet manifold is determined by the ground-state polarization, and we show successful optical read-out of the ground-state spin following microwave manipulations by fluorescence-detected magnetic resonance spectroscopy. At 85 K, the lifetime of the polarized ground state is 45 ± 3 μs, and the ground state phase memory time is Tm = 5.9 ± 0.1 μs, which increases to 26.8 ± 1.6 μs at 5 K. These results show that luminescent diradicals with triplet ground states can serve as optically addressable molecular qubits with long spin coherence times, which marks an important step toward the rational design of spin-optical interfaces in organic materials.

Boron and carbon in two-dimensional nitrogene structures: Heterodoping, doping, and chemical functionalization

We perform density functional calculations to determine the effects of simultaneous doping with carbon (C) and boron (B) on the electronic properties of nitrogene. Our procedure substitutionally incorporates the two dopants into the nitrogen monolayer. We analyze the relative position between dopants by considering different configurations. Band structure, density of states, band gaps, magnetic stability energies (energy difference between states with total magnetization with spin S=1 and S=0), and energetic stability were examined. The codoped structures exhibit a spin−dependent band gap with a strength of 1.04–2.68 eV, which is reduced compared to that in nitrogene (3.80 eV). The B-C codoped nitrogene incorporated ferromagnetism with well-localized flat bands around the Fermi level. A spin−polarized ground state was exhibited by the systems with a total magnetization of S=1, in which magnetic moments were localized mainly at the C atom and its first neighbors. The systems displayed an antiferromagnetic ordering when the total spin was fixed to S=0. The valence band maximum (VBM) was dominated by spin−up, while the conduction band minimum (CBM) was dominated by spin−down. Dopants placed as second neighbors in the nitrogene structures exhibited the most prominent band gap and magnetic stability.

Candidate ferroelectrics via ab initio high-throughput screening of polar materials

Ferroelectrics are a class of polar and switchable functional materials with diverse applications, from microelectronics to energy conversion. Computational searches for new ferroelectric materials have been constrained by accurate prediction of the polarization and switchability with electric field, properties that, in principle, require a comparison with a nonpolar phase whose atomic-scale unit cell is continuously deformable from the polar ground state. For most polar materials, such a higher-symmetry nonpolar phase does not exist or is unknown. Here, we introduce a general high-throughput workflow that screens polar materials as potential ferroelectrics. We demonstrate our workflow on 1978 polar structures in the Materials Project database, for which we automatically generate a nonpolar reference structure using pseudosymmetries, and then compute the polarization difference and energy barrier between polar and nonpolar phases, comparing the predicted values to known ferroelectrics. Focusing on a subset of 182 potential ferroelectrics, we implement a systematic ranking strategy that prioritizes candidates with large polarization and small polar-nonpolar energy differences. To assess stability and synthesizability, we combine information including the computed formation energy above the convex hull, the Inorganic Crystal Structure Database id number, a previously reported machine learning-based synthesizability score, and ab initio phonon band structures. To distinguish between previously reported ferroelectrics, materials known for alternative applications, and lesser-known materials, we combine this ranking with a survey of the existing literature on these candidates through Google Scholar and Scopus databases, revealing ~130 promising materials uninvestigated as ferroelectric. Our workflow and large-scale high-throughput screening lays the groundwork for the discovery of novel ferroelectrics, revealing numerous candidates materials for future experimental and theoretical endeavors.

Temperature-Dependent Contact of Weakly Interacting Single-Component Fermi Gases and Loss Rate of Degenerate Polar Molecules.

Motivated by the experimental realization of single-component degenerate Fermi gases of polar ground state KRb molecules with intrinsic two-body losses [L. De Marco et al., A degenerate Fermi gas of polar molecules, Science 363, 853 (2019).SCIEAS0036-807510.1126/science.aau7230], this work studies the finite-temperature loss rate of single-component Fermi gases with weak interactions. First, we establish a relationship between the two-body loss rate and the p-wave contact. Second, we evaluate the contact of the homogeneous system in the low-temperature regime using p-wave Fermi liquid theory and in the high-temperature regime using the second-order virial expansion. Third, conjecturing that there are no phase transitions between the two temperature regimes, we smoothly interpolate the results to intermediate temperatures. It is found that the contact is constant at temperatures close to zero and increases first quadratically with increasing temperature and finally-in agreement with the Bethe-Wigner threshold law-linearly at high temperatures. Fourth, applying the local-density approximation, we obtain the loss-rate coefficient for the harmonically trapped system, reproducing the experimental KRb loss measurements within a unified theoretical framework over a wide temperature regime without fitting parameters. Our results for the contact are not only applicable to molecular p-wave gases but also to atomic single-component Fermi gases, such as ^{40}K and ^{6}Li.

Distribution of Bipartite and Tripartite Entanglement within a Spin-1/2 Heisenberg Star in a Magnetic Field.

The spatial distribution of entanglement within a spin-1/2 Heisenberg star composed from a single central spin and three peripheral spins is examined in the presence of an external magnetic field using the Kambe projection method, which allows an exact calculation of the bipartite and tripartite negativity serving as a measure of the bipartite and tripartite entanglement. Apart from a fully separable polarized ground state emergent at high-enough magnetic fields, the spin-1/2 Heisenberg star exhibits at lower magnetic fields three outstanding nonseparable ground states. The first quantum ground state exhibits the bipartite and tripartite entanglement over all possible decompositions of the spin star into any pair or triad of spins, whereby the bipartite and tripartite entanglement between the central and peripheral spins dominates over that between the peripheral spins. The second quantum ground state has a remarkably strong tripartite entanglement between any triad of spins in spite of the lack of bipartite entanglement. The central spin of the spin star is separable from the remaining three peripheral spins within the third quantum ground state, where the peripheral spins are subject to the strongest tripartite entanglement arising from a two-fold degenerate W-state.

Vortex states in a PbTiO$_3$ ferroelectric cylinder

The past decade’s discovery of topological excitations in nanoscale ferroelectrics has turned the prevailing view that the polar ground state in these materials is uniform. However, the systematic understanding of the topological polar structures in ferroelectrics is still on track. Here we study stable vortex-like textures of polarization in the nanocylinders of ferroelectric PbTiO_33, arising due to the competition of the elastic and electrostatic interactions. Using the phase-field numerical modeling and analytical calculations, we show that the orientation of the vortex core with respect to the cylinder axis is tuned by the geometrical parameters and temperature of the system.

Orbital polarization change and magnetic enhancement in rutile MnO2-δ epitaxial films

Effectively manipulating the orbital configuration is an emerging method to design quantum functional materials with novel electronic ground states. Here, we report the realization of orbital polarization change in rutile MnO2-δ epitaxial thin films by reductive treatments such as CaH2 coating annealing and hydrogen atmosphere annealing. These treated samples show significant lattice expansion due to the generation of oxygen vacancies and incorporation of H, and the mixed valence states of Mn2+ and Mn3+ are formed with the decrease in the Mn valence state. The X-ray linear dichroism results show that the electron occupied state of Mn in the treated film samples changes from 3d3z2-r2 to 3dx2-y2, which means that the deprivation of oxygen atoms in the oxygen octahedron of MnO6 causes a change of orbital polarization. The resulting high spin state in the treated MnO2-δ films greatly enhances the magnetic properties of the films. This work not only demonstrates how the oxygen atoms in the edge-shared oxygen octahedron of rutile structures are replaced by reduction but also extends the study of orbital polarization and magnetic ground state control in oxide epitaxial films.

Quantum simulator of extended bipartite Hubbard model with broken sublattice symmetry: Magnetism, correlations, and phase transitions

We describe here a quantum simulator of extended bipartite Hubbard model with broken sublattice symmetry. The simulator consists of a structured lateral gate confining two dimensional electrons in a quantum well into artificial minima arranged in a hexagonal lattice. The sublattice symmetry breaking is generated by forming an artificial triangular graphene quantum dot (ATGQD) with zigzag edges. The resulting extended Hubbard model generates tunable ratio of tunneling strength to electron-electron interactions and of sublattice symmetry with control over shape. The validity of the simulator is confirmed for small systems using mean-field and exact diagonalization many-body approaches which show that the ground state changes from a metallic to an antiferromagnetic (AF) phase by varying the distance between sites or depth of the confining potential. The one-electron spectrum of these triangular dots contains a macroscopically degenerate shell at the Fermi level. The shell persists at the mean-field level for weak interactions (metallic phase) but disappears for strong interactions, in the AF phase. We determine the effects of electron-electron interactions on the ground state, the total spin, and the excitation spectrum as a function of filling of the ATGQD. We find that the half-filled charge neutral shell leads to a partially spin polarized state in both metallic and AF regimes in accordance with Liebs theorem. In both regimes a relatively large gap separates the spin polarized ground state to the first excited many-body state at half filling of the degenerate shell. By adding or removing an electron, this gap drops dramatically, and alternate total spin states emerge with energies nearly degenerate to a spin polarized ground state.

Spin-Valley Relaxation and Exciton-Induced Depolarization Dynamics of Landau-Quantized Electrons in MoSe2 Monolayer

Nonequilibrium dynamics of strongly correlated systems constitutes a fascinating problem of condensed matter physics with many open questions. Here, we investigate the relaxation dynamics of Landau-quantized electron system into spin-valley polarized ground state in a gate-tunable MoSe_{2} monolayer subjected to a strong magnetic field. The system is driven out of equilibrium with optically injected excitons that depolarize the electron spins and the subsequent electron spin-valley relaxation is probed in time-resolved experiments. We demonstrate that both the relaxation and light-induced depolarization rates at millikelvin temperatures sensitively depend on the Landau level filling factor: the relaxation is enhanced whenever the electrons form an integer quantum Hall liquid and slows down appreciably at noninteger fillings, while the depolarization rate exhibits an opposite behavior. Our findings suggest that spin-valley dynamics may be used as a tool to investigate the interplay between the effects of disorder and strong interactions in the electronic ground state.

Effect of positional isomerism on the functional properties of carbazole-phenanthroimidazole-triphenylamine triads

A series of bipolar 2, 6 or 2, 7 substituted carbazole-based isomeric hybrids featuring phenanthroimidazole as acceptor and N-phenylcarbazole or triphenylamine as donor are synthesized. Structure-property relationship of these blue-emitting materials is established by detailed investigation of physiochemical, thermal and electroluminescence characteristics. The materials showed tunable absorption and emission spectra depending upon nature and position of chromophores attached to carbazole core. The triphenylamine substituted isomers exhibited red-shifted absorption and emission spectra when compared to their respective N-phenylcarbazole-based analogs. It is attributed to the increased intramolecular charge transfer (ICT) in the electron-rich triphenylamine derivatives as further confirmed in solvatochromism studies. However, the N-phenylcarbazole derivatives showed less solvent dependence in spectra attesting less polar ground and excited state due to comparatively poor donor strength of N-phenylcarbazole. Similarly, dyes containing electron-rich chromophores showed facile removal of electron with low oxidation potentials. The thermal robustness of the compounds was attested by high thermal decomposition temperatures (Td) which varied from 438 to 481 οC. The EL performance of 3 wt% doped device fabricated with emitter derived from 2,7-disubstituted carbazole featuring N-phenylcarbazole and PI chromophores showed deep-blue CIE coordinates of (0.16, 0.06) and maximum external quantum efficiency of 5.3%.

Multiferroic ground states in free standing perovskite-based nanodots: a density functional theory study

We use density functional theory to investigate the possibility of polar and multiferroic states in free-standing, perovskite-based nanodots at the atomic limit of miniaturization: single unit cells with terminations which allow centro-symmetry. We consider both A-O and B-O2 terminations for three families of nanodots: (i) A = Ba with B = Ti, Zr, and Hf; (ii) A = Ca and Sr with B = Ti; and (iii) A = Na and K with B = Nb. We find all A–O terminated dots to be non-polar and to exhibit cubic symmetry (except for K8NbO6), regardless of the presence of ferroelectricity in the bulk. In contrast, all the B–O2 terminated nanodots considered relax to a non-cubic ground state. Rather surprisingly, all of these structures exhibit polar ground states (except NaNb8O12). We propose a new structural parameter, the cluster tolerance factor (CTF), to determine whether a particular chemistry will result in a polar ground state nanodot, analogous to the Goldschmidt factor for bulk ferroelectrics. In addition, we find that all A–O terminated (except Ca8TiO6) and all polar B–O2 terminated nanodots are magnetic, where none show magnetism in the bulk. As with bulk systems, multiferroicity in the B–O2 terminated dots originates from separation between spin density in peripheral B atoms and polarity primarily caused by the off-center central A atom. Our findings stress that surface termination plays a crucial role in determining whether ferroelectricity is completely suppressed in perovskite-based materials at their limit of miniaturization.

Transitions intensities and cross-sections of Tb3+ ions in YAl3(BO3)4 crystal

A Tb3+:YAB crystal was grown using a high-temperature solution growth on dipped seeds technique. Polarized ground state absorption and fluorescence spectra from the 5D4 level, as well as a fluorescence decay curves of 5D4 and 5D3 levels, were recorded at room temperature. Radiative properties such as emission probabilities, branching ratios, and radiative lifetime were investigated within the theory of 4f-4f transition intensity in the case of the intermediate configuration interaction.

Exploring the A2BX3 Family for New Functional Materials Using Crystallographic Database Mining and First-Principles Calculations

Ferroelectrics (FEs) are increasingly finding use as solar energy conversion materials. One of the hallmark signatures of a proper FE is a polar ground state whose polarization can be switched thro...

Investigation on Y-shaped tri-fluoromethyl substituted quinoxalines: synthesis, optical and morphological studies

Y-shaped tri-fluoromethyl substituted quinoxaline derivatives 2,3-bis(4-methoxyphenyl)-6-(trifluoromethyl)quinoxaline (1) and 2,3-bis((E)-4-methoxystryryl)-6-(trifluoromethyl)quinoxaline (2) have been synthesized and characterized using various analytical and spectroscopic techniques (1H,13C, 19F NMR, FT-IR and HR-Mass). Optical properties such as absorption, emission, quantum yield, effect of solvent polarities and Aggregation Induced Emission (AIE) have been illustrated. The compound 1 exhibited negative solvatochromism and compound 2 positive solvatochromism which are in correlation with π* values by Kamlet and Taft. Compounds 1 and 2 showed large Stoke’s shifts attributed to more polar excited state of the compounds as compared to that of polar ground state, due to the presence of electron withdrawing trifluoromethyl group. Both the compounds displayed fluorescence in solid state and AIE state due to the restricted intramolecular rotation. The compounds 1 and 2 exhibited low quantum yields because of ICT (Intramolecular charge transfer) attributed to the presence of electron-donating methoxy phenyl unit and an electron-withdrawing quinoxaline unit. AIE exhibited by both the compounds in THF/water mixture were due to the formation of nano-aggregates, it is further characterised by DLS and determined the particle size to be 196.8 nm for compound 1 and 197.3 nm for compound 2. Compound 1 appeared as ice flakes and compound 2 as a cluster consisting of various micro crystals like projections in the images determined by scanning electron microscope (SEM).

Stability and absence of a tower of states in ferrimagnets

Antiferromagnets and ferromagnets are archetypes of the two distinct (type-A and type-B) ways of spontaneously breaking a continuous symmetry. Although type-B Nambu--Goldstone modes arise in various systems, the ferromagnet was considered pathological due to the stability and symmetry-breaking nature of its exact ground state. However, here we show that symmetry-breaking in ferrimagnets closely resembles the ferromagnet. In particular, there is an extensive ground state degeneracy, there is no Anderson tower of states, and the maximally polarized ground state is thermodynamically stable. Our results are derived analytically for the Lieb--Mattis ferrimagnet and numerically for the Heisenberg ferrimagnet. We argue that these properties are generic for type-B symmetry-broken systems, where the order parameter operator is a symmetry generator.

Collective spin density excitation of fractional quantum Hall states in dilute ultra-cold Bose atoms

We have studied collective spin density excitation of fractional quantum Hall effect (FQHE) in rotating Bose–Einstein condensation for the three filling fractions of first series of Jain’s composite fermion sequences. We have considered short-ranged contact interactions between the Bose atoms as well as long range Coulomb interactions to compare the nature of the spectra with FQHE of electrons. Using Monte-Carlo method for finite but large number of particles, the lowest order collective modes of spin-reversed sectors is calculated here, by computing the energy differences of the respective excitons from the fully polarized ground states.

First principles study on hydrogen storage in yttrium doped graphyne: Role of acetylene linkage in enhancing hydrogen storage

Through Density Functional Theory Simulations we predict that a Ytrrium atom attached on graphyne surface can adsorb up to a maximum of 9 molecular hydrogens (H2), with a uniform binding energy of ∼0.3 eV/H2 and an average desorption temperature of around 400 K (ideal for fuel cell applications), leading to 10 wt% of hydrogen, substantially higher than the requirement by DoE. The higher hydrogen wt% in Y doped graphyne compared to Y doped Single Walled Carbon Nanotubes (SWNT) and graphene is due to the presence of sp hybridized C atoms (in the acetylene linkage) supplying additional in-plane px-py orbitals leading to π (π*) bonding (antibonding) states. Charge transfer from metal to carbon nanostructure results in a redistribution of s, p, d orbitals of the metal leading to a non - spin polarized ground state in Y doped graphyne, due to the presence of the acetylene linkage, whereas Y doped SWNT and graphene remain magnetic like the isolated metal atom. In the non-magnetic graphyne + Y system, the net charge transfer from Y to successive H2 molecules is less than in magnetic Y + graphene and Y + SWNT systems, enabling Y + graphyne to store a larger number of H2 molecules. Furthermore, our ab initio MD simulations show that the system is stable even at room temperature and there is no dissociation of H2 molecules, enabling the system to achieve 100% desorption. So Y doped graphyne is found to be a promising hydrogen storage device with high wt%, 100% recyclability and desirable desorption temperature.

Cross sections and transition intensities of Tb3+ in KY(WO4)2

A Tb3+:KYW crystal was grown by the modified Czochralski technique. Polarized ground state absorption and fluorescence spectra, as well as a fluorescence decay curve, were recorded at room temperature. Radiative properties such as emission probabilities, branching ratios, and radiative lifetime were investigated within the theory of 4f–4f transition intensity in the case of a strong configuration interaction. The limitations of visible laser operation of Tb3+-doped double tungstate crystals are discussed.

Variation of Donor and Acceptor Strength in Analogues of Brooker's Merocyanine and Generalization to Various Classes of Charge Transfer Compounds.

Derivatives of Brooker's merocyanine (BM) have been investigated, which possess different donors and acceptors and therefore vary their donor-acceptor strength SDA. The 00 energies have been extracted from the spectra and compared. Under basic conditions, where the neutral (merocyanine) form is present, the absorption energies for all compounds are similar, whereas there is a large difference for acidic conditions where the cationic (cyanine) form is present. This behavior could be explained by a simple theoretical model involving the dependence of the excitation energy Δ E01 on SDA. This model can be generalized to describe in a consistent way two different well-known classes of neutral chromophores with a certain degree of charge separation, namely merocyanine I (TICT) and merocyanine II (often betainic) compounds. Merocyanines I are characterized by a medium polar aromatic ground state and a zwitterionic quinoid excited state and hence positive solvatochromism, whereas merocyanines II are formally characterized by a zwitterionic aromatic ground state and a less polar quinoid excited state and, accordingly, by negative solvatochromism. On increasing the donor-acceptor strength SDA sufficiently, merocyanines II can, however, move to the so-called overcritical region with the excited state dominated by the zwitterionic valence bond structure. For many of the merocyanine II molecules investigated here, a weakly positive solvatochromic behavior is observed indicating that the ground state contains less of the zwitterionic valence bond wave function than the excited state and that these compounds belong to the overcritical region. The fluorescence spectra have been analyzed in terms of the Franck-Condon model and confirm these conclusions.

Metastable hard-axis polar state of a spinor Bose-Einstein condensate under a magnetic field gradient

We investigate the stability of a hard-axis polar state in a spin-1 antiferromagnetic Bose-Einstein condensate under a magnetic field gradient, where the easy-plane spin anisotropy is controlled by a negative quadratic Zeeman energy $q<0$. In a uniform magnetic field, the axial polar state is dynamically unstable and relaxes into the planar polar ground state. However, under a field gradient $B'$, the excited spin state becomes metastable down to a certain threshold $q_{th}$ and as $q$ decreases below $q_{th}$, its intrinsic dynamical instability is rapidly recalled. The incipient spin excitations in the relaxation dynamics appear with stripe structures, indicating the rotational symmetry breaking by the field gradient. We measure the dependences of $q_{th}$ on $B'$ and the sample size, and we find that $q_{th}$ is highly sensitive to the field gradient in the vicinity of $B'=0$, exhibiting power-law behavior of $|q_{th}|\propto B'^{\alpha}$ with $\alpha \sim 0.5$. Our results demonstrate the significance of the field gradient effect in the quantum critical dynamics of spinor condensates.