Stable Spin States Research Articles

Electronic Properties of the Co3O4 Photoelectrode: Predictions from First-Principles Calculations

Cobalt Oxide (Co3O4) has emerged as a highly promising material for hydrogen generation through photoelectrochemical cells (PECs); however, a detailed understanding of the electronic properties of this material is largely lacking. This includes the band gap and electrical conductivity of the photoelectrode, which are important factors in determining the performance of PECs. For example, contradicting experimental results have been reported for the optical gap of Co3O4, leading to two commonly reported values of 0.8 eV and 1.6 eV. In this work, we have employed first-principles calculations based on Density Functional Theory to support that the intrinsic band gap of Co3O4 is 1.6 eV. Meanwhile, we show that the 0.8 eV transition found experimentally is due to the presence of polaron or defect states. In particular, our calculations predict the spontaneous formation of electron and hole polarons, that in turn exhibit significant contribution to the absorption spectra of the material, and are responsible for the optical excitation at 0.8 eV. Finally, we resolve the nature of the stable spin states of electron and hole polarons, and we discuss how the interaction between polarons with n-type dopants, such as carbon, could improve the electrical conductivity of this intrinsic p-type material. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Influence of Spin State and Cation Distribution on Stability and Electronic Properties of Ternary Transition-Metal Oxides.

This work is a systematic ab initio study of the influence of spin state and cation distribution on the stability, dielectric constant, electronic band gap, and density of states of ternary transition-metal oxides. As an example, the chemical family of spinel ferrites MFe2O4, with M = Mg, Sc–Zn is chosen. Dielectric constant and band gap are calculated for various spin states and cation configurations via dielectric-dependent self-consistent hybrid functionals and compared to available experimental data. When choosing the most stable spin state and cation configuration, the calculated electronic properties are in reasonable agreement with measured values. The nature of the excitation is investigated through projected density of states. A pronounced dependence of band gap energy and dielectric constant on the spin state and cation configuration is observed, which is a possible explanation for the large variation of the experimental results, in particular, if several states are energetically close.

Lead-related quantum emitters in diamond

We report on quantum emission from Pb-related color centers in diamond following ion implantation and high temperature vacuum annealing. First-principles calculations predict a negatively-charged Pb-vacancy center in a split-vacancy configuration, with a zero-phonon transition around 2.3 eV. Cryogenic photoluminescence measurements performed on emitters in nanofabricated pillars reveal several transitions, including a prominent doublet near 520 nm. The splitting of this doublet, 2 THz, exceeds that reported for other group-IV centers. These observations are consistent with the PbV center, which is expected to have the combination of narrow optical transitions and stable spin states, making it a promising system for quantum network nodes.

Spin Polarization and Magnetic Properties of VGaON and VGaONInGa in GaN: GGA+U Approach

Electronic structure of a defect center containing the gallium vacancy and substitutional oxygen atom at nitrogen site (VGaON) in zinc blende and wurtzite GaN was analyzed within GGA+U approach. The +U term was applied to d(Ga), p(N), p(O), and d(In). Neutral VGaON is in the stable high spin state with spin S = 1. The defect structure is strongly dependent on geometry of the defect and the charge state. Two spin structures, which arise due to two different configurations in VGaON, with ON either along the c-axis or in one of three equivalent tetrahedral positions in wurtzite structure were analyzed. The weak ferromagnetic coupling between centers was found. The strength of magnetic coupling is increased when there is a complex containing VGaON with additional substitutional indium atom at the second neighbor to vacancy gallium site (VGaONInGa). Magnetic coupling between VGaONInGa is ferromagnetic due to strong spin polarization of p electrons of the nearest and distant nitrogen atoms.

Theoretical insight into structural and electronic properties of cationic Scn+ (n=2-13): A benchmark study

Geometric, thermodynamic and electronic properties of cationic scandium clusters are studied. Geometric optimizations and stable spin states of Sc2+ are assessed on high level ab-initio coupled cluster method CCSD(T) with different dunning correlation consistent basis sets (aug-cc-pVDZ, aug-cc-pVTZ and aug-cc-pVQZ). Then, 23 DFT functionals belonging to different classes are evaluated at 6-31G (d), LANL2MB, LANL2DZ and Def2-SVP basis sets, and the results are compared with the benchmarked coupled cluster calculations. Due to excellent correlation, PBEPBE/LANL2DZ was chosen to perform calculation of higher scandium cationic clusters Scn+ (n = 3-13). In addition, we explored relative stability, binding energies, second order energy differences, vertical ionization energies, vertical electron affinities and HOMO-LUMO gaps. Moreover, these results are also compared with the neutral scandium clusters.

Hydrodynamic spin states.

We present the results of a theoretical investigation of hydrodynamic spin states, wherein a droplet walking on a vertically vibrating fluid bath executes orbital motion despite the absence of an applied external field. In this regime, the walker's self-generated wave force is sufficiently strong to confine the walker to a circular orbit. We use an integro-differential trajectory equation for the droplet's horizontal motion to specify the parameter regimes for which the innermost spin state can be stabilized. Stable spin states are shown to exhibit an analog of the Zeeman effect from quantum mechanics when they are placed in a rotating frame.

First-principles engineering of charged defects for two-dimensional quantum technologies

Charged defects in 2D materials have emerging applications in quantum technologies such as quantum emitters and quantum computation. Advancement of these technologies requires rational design of ideal defect centers, demanding reliable computation methods for quantitatively accurate prediction of defect properties. We present an accurate, parameter-free and efficient procedure to evaluate quasiparticle defect states and thermodynamic charge transition levels of defects in 2D materials. Importantly, we solve critical issues that stem from the strongly anisotropic screening in 2D materials, that have so far precluded accurate prediction of charge transition levels in these materials. Using this procedure, we investigate various defects in monolayer hexagonal boron nitride (h-BN) for their charge transition levels, stable spin states and optical excitations. We identify $C_BN_V$ (nitrogen vacancy adjacent to carbon substitution of boron) to be the most promising defect candidate for scalable quantum bit and emitter applications.

Tidal effects in differentiated viscoelastic bodies: a numerical approach

The majority of confirmed terrestrial exoplanets orbits close to their host stars and their evolution was likely altered by tidal interaction. Nevertheless, due to their viscoelastic properties on the tidal frequencies, their response cannot be described exactly by standardly employed constant-lag models. We therefore introduce a tidal model based on the numerical evaluation of a continuum mechanics problem describing the deformation of viscoelastic (Maxwell or Andrade) planetary mantles subjected to external force. We apply the method on a model Earth-size planet orbiting a low-mass star and study the effect of the orbital eccentricity, the mantle viscosity and the chosen rheology on the tidal dissipation, the complex Love numbers and the tidal torque. The number of stable spin states (i.e., zero tidal torque) grows with increasing mantle viscosity, similarly to the analytical model of Correia et al. (Astron Astrophys 571:A50, 2014) for homogeneous bodies. This behavior is only slightly influenced by the rheology used. Similarly, the Love numbers do not distinctly depend on the considered rheological model. The increase in viscosity affects the amplitude of their variations. The tidal heating described by the Maxwell rheology attains local minima associated with low spin-orbit resonances, with depth and shape depending on both the eccentricity and the viscosity. For the Andrade rheology, the minima at low resonances are very shallow and the tidal heating for all viscosities resembles a “fluid limit.” The tidal heating is the quantity influenced the most by the rheology, having thus possible impact on the internal thermal evolution.

Benchmark study of structural and vibrational properties of scandium clusters

Geometries and most stable spin states of Sc2 and Sc3 are studied through coupled cluster CCSD(T) calculations. The CCSD(T) calculations at dunning series basis sets (aug-cc-pVDZ, aug-cc-pVTZ and aug-cc-pVQZ) have been performed in order to analyze the stable structure and spin state of the Sc2 and Sc3. Then, a series of diverse DFT methods at different basis sets (6-31G (d), LANL2DZ and LANL2MB) are assessed for structural and vibrational properties in order to propose low cost accurate alternative to CCSD(T). Among all the employed DFT methods, BPV86/LANL2MB delivered better results for structural and frequency analysis. On the basis of better agreement, BPV86/LANL2MB is taken for the structural and vibrational analysis of the higher cluster n = 4–14. The vibrational analysis for higher clusters of scandium is reported for the first time.

Electronic Structure of Iron Porphyrin Adsorbed to the Pt(111) Surface

Systematic density functional theory calculations that treat the strong on-site 3d electron–electron interactions on iron via a Hubbard Ueff = 3.0 eV and the van der Waals (vdW) interactions between the substrate and adsorbate within the vdW-DF framework are employed to study the adsorption of the iron porphyrin (FeP) molecule to the Pt(111) surface. The more accurate vdW-DF-optPBE and vdW-DF-optB88 functionals found the same binding site to be the most stable and yielded binding energies that were within ∼20% of each other, whereas the binding energies computed with the vdW-DF-revPBE functional were substantially weaker. This work highlights the importance of vdW interactions for organometallic molecules chemisorbed to transition metal surfaces. The stability of the binding sites was found to depend upon the number of Fe–Pt and C–Pt bonds that were formed. Whereas in the gas phase the most stable spin state of FeP is the intermediate spin S = 1 state, the high spin S = 2 state is preferred for the FeP–Pt...

Spin-Spin Coupling in Nitrogen Atom Encapsulated C60, C59N, and Their Respective Dimers.

Density functional theoretical calculations were performed to study the stability and magnetic properties of nitrogen-encapsulated C60, C59N, and their respective dimers at B3LYP/6-311G* and B3LYP-GD2/6-311G* levels of theory. For the most stable spin state of each of the above complexes, spin density transfer and spin-spin coupling between different components are investigated. The nature of bonding between the guest and the host is analyzed based on the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap and the respective molecular orbital diagrams. The analysis of spin density showed that the encapsulated nitrogen retained its atomic state in N@C60 and N@C59N. Depending on the multiplicity of N@C59N, the unpaired electrons of the encapsulated nitrogen are coupled with those of the cage anti-ferromagnetically or ferromagnetically. The present study also showed that the complex (N@C60)2 can exist in two isoenergetic spin states, namely, (7)[(N@C60)2] and (1)[(N@C60)2]. In the former, the encapsulated nitrogens are ferromagnetically coupled, whereas they are coupled anti-ferromagnetically in the latter. A similar coupling between the guest species occurs in the nitrogen analogues (7)[(N@C59N)2] and (1)[(N@C59N)2]. The stabilization energy of the endohedral nitrogen complexes indicated that the interaction between the guest and the host cage is purely noncovalent.

Effect of Surface Site on the Spin State for the Interaction of NO with Pd<sub>2</sub>, Rh<sub>2</sub> and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

An attempt has been made to analyze the effect of surface site on the spin state for the interaction of NO with Pd2, Rh2 and PdRh nanoparticles that supported at regular and defective MgO(001) surfaces. The adsorption properties of NO on homonuclear, Pd2, Rh2, and heteronuclear transition metal dimers, PdRh, that deposited on MgO(001) surface have been studied by means of hybrid density functional theory calculations and embedded cluster model. The most stable NO chemisorption geometry is in a bridge position on Pd2 and a top configuration of Rh2 and PdRh with N-down oriented. NO prefers binding to Rh site when both Rh and Pd atoms co-exist in the PdRh. The natural bond orbital analysis (NBO) reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The adsorption properties of NO have been analyzed with reference to the NBO, charge transfer, band gaps, pairwise and non-pairwise additivity. The binding of NO precursor is dominated by the E(i)Mx-NO pairwise additive components and the role of the support was not restricted to supporting the metal. The adsorbed dimers on the MgO surface lose most of the metal-metal interaction due to the relatively strong bond with the substrate. Spin polarized calculations were performed and the results concern the systems in their more stable spin states. Spin quenching occurs for Rh atom, Pd2, Rh2 and PdRh complexes at the terrace and defective surfaces. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support and dimer-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals and dimers. Although the interaction of Pd, Rh, Pd2, Rh2 and PdRh particles with Fs sites is much stronger than the regular sites O2-, the adsorption of NO is stronger when the particular dimers are supported on an anionic site than on an Fs site of the MgO(001). The encountered variations in magnetic properties of the adsorbed species at MgO(001) surface are correlated with the energy gaps of the frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules on the magnetic and binding properties of complexes need to be explicitly taken into account.

Spin-transfer torque and specific features of magnetic-state switching in vacuum tunnel nanostructures

The specific features of spin-transfer torque in vacuum tunnel structures with magnetic electrodes are investigated using the quasi-classical Sommerfeld model of electron conductivity, which takes into account the exchange splitting of the spin energy subbands of free electrons. Using the calculated voltage dependences of the transferred torques for a tunnel structure with cobalt electrodes and noncollinear magnetic moments in the electrodes, diagrams of stable spin states on the current–field parameter plane in the in-plane geometry of the initial magnetization are obtained.

Unidirectional electric field-induced spin-state switching in spin crossover based microelectronic devices

We report on a molecular spin-state switching phenomenon induced by an electric field in micrometric objects of the [Fe(Htrz)2(trz)](BF4) spin crossover complex, organized between interdigitated electrodes. By applying an electric field step of 40kV/cm at temperatures within the thermal hysteresis region of the first-order spin transition, the iron(II) ions are switched from the metastable high spin to the stable low spin state obtaining a rather incomplete transition but perfectly reversible by heating. A model based on the interaction between the electric field and the electric dipolar moment of spin crossover complexes, grasps the main features of the experimental data.

Revealing Defects in Crystalline Lithium-Ion Battery Electrodes by Solid-State NMR: Applications to LiVPO4F

Identifying and characterizing defects in crystalline solids is a challenging problem, particularly for lithium-ion intercalation materials, which often exhibit multiple stable oxidation and spin states as well as local ordering of lithium and charges. Here, we reveal the existence of characteristic lithium defect environments in the crystalline lithium-ion battery electrode LiVPO4F and establish the relative subnanometer-scale proximities between them. Well-crystallized LiVPO4F samples were synthesized with the expected tavorite-like structure, as established by X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) measurements. Solid-state 7Li nuclear magnetic resonance (NMR) spectra reveal unexpected paramagnetic 7Li environments that can account for up to 20% of the total lithium content. Multidimensional and site-selective solid-state 7Li NMR experiments using finite-pulse radio frequency-driven recoupling (fp-RFDR) establish unambiguously that the unexpected lithium environmen...

Stable spin states of boron, aluminum and silicon dimers in a self-consistent GW calculation

Some small clusters, in particular dimers (diatomic molecules), composed of nonmagnetic atoms exhibit intrinsic spin magnetic moments. In this paper, we discuss the most stable spin state of boron, aluminum and silicon dimers. In order to treat the dynamically screened exchange interaction between electrons correctly, we adopt the self-consistent GW approximation in many-body perturbation theory. We find that the energy gain of the triplet ground state from the singlet excited state as a reference is mainly caused by the dynamically screened exchange interaction, although other contributions to the total energy do not have the same tendency between the triplet and singlet states. We also explicitly show the resulting quasiparticle energy spectra which can be compared with the photoemission and inverse photoemission spectroscopy measurements.

Spectroscopic characteristics of the cyanomethyl anion and its deuterated derivatives

It has long been suggested that CH2CN- might be a carrier of one of the many poorly characterized diffuse interstellar bands. In this paper, our aim is to study various forms of CH2CN in the interstellar medium. Aim of this paper is to predict spectroscopic characteristics of various forms of CH2CN and its deuterated derivatives. Moreover, we would like to model the interstellar chemistry for making predictions for the column densities of such species around dark cloud conditions. A detailed quantum chemical simulations to present the spectral properties of various forms of the CH2CN. MP2 theory along with the aug-CCPVTZ basis set is used to obtain different spectroscopic constants of CH2CN-, CHDCN- and CD2CN- in the gas phase which are essential to predict rotational spectra of these species. We performed quantum chemical calculation to find out energetically the most stable spin states for these species. We have computed IR and electronic absorption spectra for different forms of CH2CN. Moreover, we have also implemented a large gas-grain chemical network to predict the column densities of various forms of the cyanomethyl radical and its related species. In order to mimic physical conditions around a dense cloud region, the variation of the visual extinction parameters are considered with respect to the hydrogen number density of the simulated cloud. Our quantum chemical calculation reveals that the singlet spin state is the most stable form of cyanomethyl anion and its deuterated forms. For the confirmation of the detection of the cyanomethyl anion and its two deuterated forms, namely, CHDCN- and CD2CN-, we present the rotational spectral information of these species in the Appendix. Our chemical model predicts that the deuterated forms of cyanomethyl radicals (specially the anions) are also reasonably abundant around the dense region of the molecular cloud.

A combined first principles TDDFT and experimental study on the UV-Vis spectra properties of M(p-nitrophenyl azo resorcinol)$_{3}$ complexes (M: Fe, Cr)

UV-Vis absorption data of p-nitrophenyl azo resorcinol (Magneson I) and its 2 Fe(III) and Cr(III) complexes were investigated both experimentally and theoretically. The geometries were optimized at BP86/TZVP level. The most stable spin states were computed as doublet and quartet for Fe(magneson)_3 and Cr(magneson)_3 complexes, respectively. Time-dependent density functional theory (TDDFT) was employed to explore the absorption spectra properties, whereas the solvent effects were taken into account using the polarizable continuum model (PCM). The M06, B3LYP, and PBE0 hybrid functionals together with TZVP/LANL2TZ basis sets were used for comparing the results with experimental data. The theoretical analysis of electronic structure and molecular orbitals demonstrated that the low-lying absorption bands in the UV-Vis spectra are mainly \pi \to d ligand-to-metal charge transfer (LMCT) transition and \pi \to \pi ligand-to-ligand charge transfer (LLCT) transition for Fe(magneson)_3, and, in addition to that of LMCT and LLCT, d \to \pi metal-to-ligand charge transfer (MLCT) transition for Cr(magneson)_3 complexes. The good agreement between the experimental and TDDFT calculation, especially M06 and B3LYP absorption spectra of the metal Magneson I complexes, allowed us to provide a detailed estimation of the main spectral features of ferric and chromic complexes.

Adsorption of NO on Pd and Pd2 supported at the regular and defective CdO (0 0 1) surfaces: Density functional theory study

The adsorption of NO on Pd atoms and homonuclear transition metal dimers, Pd2, deposited on O2− and Fs sites of the CdO (001) surface was studied by density functional calculations and an embedded cluster model. Geometrical optimization of adsorption of the molecule NO on Pd/CdO and Pd2/CdO with different spin states at particular sites was conducted. Spin polarized calculations were performed, and the systems in the most stable spin states were determined. Spin quenching occurs for Pd2 complexes at the terrace and defective surfaces. Supported Pd2 stabilized the low spin states of the adsorbed metals in comparison with free Pd2. Although the interaction of Pd and Pd2 particles with Fs sites is much stronger than with regular O2− sites, the adsorption of NO is stronger on Pd2/CdO (O2−) than on Pd2/CdO (Fs) with low spin state. Nevertheless, the greater interaction of NOPd and NOPd2 at O2− sites increases the energy required to switch from high to low spin. The variations observed in the magnetic properties of the adsorbed species at the CdO (001) surface are correlated with the energy gaps of the frontier orbitals. The adsorption properties of NO were analyzed with reference to the natural bond orbital, charge transfer, band gaps, the total charge-density contours, and pairwise and non-pairwise additivity. The binding of NO precursor is dominated by the E(i)Pdx−NO pairwise additive components, and the role of the support was not restricted to the metal or the dimer.

Ultrafast tristable spin memory of a coherent polariton gas

Non-linear interactions in coherent gases are not only at the origin of bright and dark solitons and superfluids; they also give rise to phenomena such as multistability, which hold great promise for the development of advanced photonic and spintronic devices. In particular, spinor multistability in strongly coupled semiconductor microcavities shows that the spin of hundreds of exciton-polaritons can be coherently controlled, opening the route to spin-optronic devices such as ultrafast spin memories, gates or even neuronal communication schemes. Here we demonstrate that switching between the stable spin states of a driven polariton gas can be controlled by ultrafast optical pulses. Although such a long-lived spin memory necessarily relies on strong and anisotropic spinor interactions within the coherent polariton gas, we also highlight the crucial role of non-linear losses and formation of a non-radiative particle reservoir for ultrafast spin switching.