Mixed Spin State Research Articles

Angular momentum coefficients for meson strong decay and unquenched quark models

In most meson strong decay and unquenched (coupled-channel) quark models, the pair-creation operator is a scalar product of vectors in the spin and spatial degrees of freedom. While differing in the spatial part, most models have the same spin part, which creates a qq* pair coupled to spin triplet, with the spins of the initial quarks as spectators. This is a basic assumption of the 3P0 model, and is well-known to arise also in the flux tube model, starting from the strong coupling expansion of lattice QCD. In this article the same structure is shown to emerge in the Cornell model, in the dominant contributions of a more general microscopic decay model, and in the pseudoscalar-meson emission model. A solution is obtained for arbitrary matrix elements in these ``non-flip, triplet'' models, expressed as a weighted sum over spatial matrix elements. The coefficients in the expansion, which involve the spin degrees of freedom and the associated angular momentum algebra, are model-independent. Tables of the angular momentum coefficients are presented which can be used in future calculations, avoiding tedious Clebsch-Gordan sums. The symmetry and orthogonality properties of the coefficients are discussed, as well as their application to transitions involving hybrid mesons and states of mixed spin. New selection rules are derived, and existing ones generalised. The coefficients lead to model-independent relations among decay amplitudes and widths which can be tested in experiment and lattice QCD. They can also be used to explain how mass shifts in the unquenched quark model do not spoil successful predictions of the ordinary (quenched) quark model.

Longitudinal–transversal polariton splitting on a GaAs single quantum well microcavity

Exciton polariton is a quasi-particle formed in a microcavity, which keeps the exciton and the photon property, e.g. the exciton longitudinal–transversal energy splitting. In this work we observed a splitting as large as 0.19meV in the polariton emission mode in a GaAs single quantum well microcavity for the heavy hole as well as a 0.137meV for the light hole excitons. The splitting behavior was analyzed as a function of excitation power and the polarization degree. The results indicate one longitudinal–transversal splitting emission light with mixed spin states and crossed linear polarizations for the longitudinal–transversal modes, and a condensation behavior only for the heavy hole transversal mode.

Tripartite Entanglement and Lorentz Transformation

Entanglement of tripartite spin states under Lorentz transformations is studied in the context of Bell’s inequality and positive partial transpose criterion. First the relativistic analogue of Bell’s inequality is discussed for three qubit states by explicit calculation of the Wigner rotation. We use the relativistic invariant spin operator which is related to the Pauli-Lubanski pseudo vector. For observers at rest the Bell’s inequality is speed-independent and maximally violated. For moving observers it’s shown that Bell’s inequality is violated and the amount of violation depends on the boost speed. We show that in ultrarelativistic limit Bell’s inequality is still maximally violated. We also obtained the critical value for satisfying Bell’s inequality. The critical value of boost speed for violation of inequality for particles moving in the center of mass frame is greater than that for particles moving with the same momentum. Second we investigate the entanglement distillability of tripartite mixed spin states under Lorentz transformations in the context of Werner states. We show that there are states that will change from distillable (entangled) into separable for a certain value of rapidity.

Photoselective DNA Hairpin Spin Switches

DNA hairpins having both a tethered anthraquinone (Aq) end-capping group and a perylenediimide (PDI) base surrogate were synthesized, wherein Aq and PDI are each separated from a G-C base pair hole trap by A-T and I-C base pairs (G = guanine, A = adenine, T= thymine, C = cytosine, I = inosine). Selective photoexcitation of PDI at 532 nm generates a singlet radical ion pair (RP), (1)(G(+•)-PDI(-•)), while selective photoexcitation of Aq at 355 nm generates the corresponding triplet RP, (3)(G(+•)-Aq(-•)). Subsequent radical pair intersystem crossing within these spin-correlated RPs leads to mixed spin states that exhibit spin-polarized, time-resolved EPR spectra in which the singlet- and triplet-initiated RPs have opposite phases. These results demonstrate that a carefully designed DNA hairpin can serve as a photodriven molecular spin switch based on wavelength-selective formation of the singlet or triplet RP without significant competition from undesired energy transfer processes.

Distinct Structural and Redox Properties of the Heme Active Site in Bacterial Dye Decolorizing Peroxidase-Type Peroxidases from Two Subfamilies: Resonance Raman and Electrochemical Study

Spectroscopic data of dye decolorizing peroxidases (DyPs) from Bacillus subtilis (BsDyP), an A subfamily member, and Pseudomonas putida (PpDyP), a B subfamily enzyme, reveal distinct heme coordination patterns of the respective active sites. In solution, both enzymes show a heterogeneous spin population, with the six-coordinated low-spin state being the most populated in the former and the five-coordinated quantum mechanically mixed-spin state in the latter. We ascribe the poor catalytic activity of BsDyP to the presence of a catalytically incompetent six-coordinated low-spin population. The spin populations of the two DyPs are sensitively dependent on the pH, temperature, and physical, i.e., solution versus crystal versus immobilized, state of the enzymes. We observe a redox potential for the Fe(2+)/Fe(3+) couple in BsDyP (-40 mV) at pH 7.6 substantially more positive than those reported for the majority of other peroxidases, including PpDyP (-260 mV). Furthermore, we evaluate the potential of the studied enzymes for biotechnological applications on the basis of electrochemical and spectroelectrochemical data.

Electronic structures and phonon free energies of LaCoO3using hybrid-exchange density functional theory

Hybrid-exchange density functional theory has been used to model the electronic structure of LaCoO${}_{3}$. Based on a rhombohedral unit cell of $R\overline{3}c$ symmetry containing two Co atoms we find a mixed spin phase, comprising alternating low and high spin Co${}^{+3}$ ions, with a total energy at 0 K just 57 meV per formula unit above that of a nonmagnetic semiconducting ground state. In the mixed spin phase the high-spin Co${}^{+3}$ ions have spin moments of $3.1\phantom{\rule{0.28em}{0ex}}{\ensuremath{\mu}}_{B}$ and the state is insulating with a band gap of 2.2 eV. Our calculations suggest that the effective on-site Coulomb repulsion energy ${U}_{\mathrm{eff}}$ on Co${}^{+3}$ ions is spin dependent. The ${U}_{\mathrm{eff}}$ on Co${}^{+3}$ ions is 7.1 eV and 8.5 eV for the nonmagnetic ground state and for the magnetic high spin state, respectively. For the mixed spin state, two different ${U}_{\mathrm{eff}}$ are estimated for two Co${}^{+3}$ ions in the unit cell having different spin states, 8.0 eV for the high-spin Co${}^{+3}$ ion and 7.0 eV for the low-spin Co${}^{+3}$ ion. An estimate of the harmonic phonon free energy suggests that this mixed spin phase would become the more stable phase as the temperature increases, which is consistent with experimental evidence. An alternative intermediate spin state is higher in energy at all temperatures.

Cation Modulation of Hemoglobin Interaction with Sodium n-Dodecyl Sulfate (SDS). III: Calcium Interaction with R- and Mixed Spin States of Hemoglobin S at pH 5.0: The Musical Chair Paradox

We investigate the interaction of Ca(2+) (0-500µM) and a membrane mimic (0.60mM SDS) with both the R- and mixed spin states hemoglobin S (HbS) as a function of time. These interactions were carried out at pH 5.0. We aim at ascertaining if there is or are differences in the UV-Visible spectra of such interactions to account for the dynamics of calcium ion concentrations [Ca(2+)] in initiating structures which may ultimately suggest HbS polymerization and or resistance to Plasmodium attack. From our results, we conclude that (a) simultaneous interaction of 40µM Ca(2+) and 0.60mM SDS with the R state protein would promote structural formations that can "lock up" the protein for nucleation on the membranes and or become cytotoxic to the parasite; (b) simultaneous R state HbS-SDS or R state HbS-Ca(2+) would lead to enhanced hemin formation and less deoxyHb species. This condition is unlikely to precipitate polymerization in the HbS but the resulting hemin would poison the parasite; (c) the mixed spin state HbS-SDS and 40µM Ca(2+) interaction yields more toxic products to that of the interaction of the mixed spin HbS-SDS with 500µM Ca(2+) thus suggesting why the 40µM Ca(2+) is important in parasite Hb proteolysis; and (d) pronounced structural changes on interaction with SDS and Ca(2+) are more in the R state to the mixed spin state.

ESR and magnetic studies of octahedral [Fe(III)(Cl)(pcd)(H2O)(DMSO)] (pcd = pyridine-2,6-dicarboxylato) compound showing Fe(III) species with different spin states in solution

By direct synthesis has been obtained the octahedral complex [Fe(III)(Cl)(pdc)(H2O)(DMSO)] 1 (pdc=pyridyn-2,6-dicarboxylato), which shows a supramolecular structure and a clear and large molecular distortion. UV–Vis spectrum of 1 shows at 741nm, 836nm (ε=100M−1cm−1) and 970nm (ε=1600M−1cm−1) typical iron d–d transitions. FIR spectrum of 1 shows vibrations υFeO, υFeN and υFeCl. NMR 1H spectroscopy is typical of paramagnetic compounds. The susceptibility data fit to a Hamiltonian, Hex=−2JS1·S2, using two models, give close exchange interaction constant values of: J=−1.803cm−1, g=1.810 and J=−1.102cm−1, g=1.832. X-band ESR spectra of powder sample of 1 at 300K/77K show broad signals at H≈56.70mT/64.53mT, characteristic of ferromagnetic absorptions. X-band spectra of 1 at 77K in methanol solution at different concentrations show typical signals of Fe(III) species with high spin, S=5/2, quantum mixed spin state (qms), 5/2, 3/2, which are present in ESR spectra of peroxidase enzymes, and a low spin S=1/2. 1 has been used as catalyst in the guaiacol test, characteristic of peroxidase enzymes, giving positive by visual observation and by UV–Vis spectroscopy. By ERS spectroscopy has been observed the characteristic π-cationic-radical ferryl, enzyme covalently modified, when the peroxidase enzyme is active. The presence of Fe(III) species with qms observed by ESR spectra of 1, and its catalytic activity, both characteristic of peroxidase enzymes, are a significant conclusion of the work.

Observation of new near infrared emission band systems of small bismuth clusters in solid neon matrix

Laser induced fluorescence (LIF) spectroscopy was applied to small bismuth clusters embedded in a solid neon matrix at 3 K. Near infrared (NIR) optical emission spectra were recorded in a range of 6200–11 600 cm-1 by an excitation with 1.79 eV photons using a pulsed dye laser system. Three new NIR band systems were identified by their origin bands at 8207, 9625 and 11 395 cm-1. Each of the NIR systems exhibited the vibrational progression with a common lower state frequency at 151 cm-1. Temporal decay profiles for selected NIR emission bands showed upper state lifetimes on the order of a hundred of microseconds, explainable by the transition between mixed spin states. Low-lying electronic states for small bismuth clusters, Bi n (n = 2 − 4), are discussed along the theory and experiment reported so far.

On the optical properties and low pressure-induced spin transition in magnetite from ab initio calculations

The electrical anomaly observed in the high-temperature phase of magnetite under pressure is studied in the framework of DFT/LSDA+U formalism. We show that the phenomenon cannot be accounted for by a coordination crossover nor by a Fe2+ high-spin (HS) to an intermediate-spin (IS) transition. We suggest the transition may be related to the formation of an inhomogeneous mixed-spin state system HS→HS/LS with cations in octahedral sites.

Lattice dynamics calculations for ferropericlase with internally consistent LDA+U method

Vibrational densities of states and phonon dispersion relations for Mg0.875Fe0.125O ferropericlase in the high‐ and low‐spin (HS and LS) states were calculated from first principles lattice dynamics using the internally consistent LDA+Utechnique. Finite‐temperature thermodynamic properties were determined based on the quasi‐harmonic approximation including the HS and LS mixing entropy and the magnetic entropy effects, which gave pressure and temperature variations of the low‐spin fraction. Our results suggest that for thermodynamic modeling of the earth's interior, the effect of the mixed spin state cannot be ignored in the lower mantle, especially the lowermost part. The anomaly in the seismic wave velocity due to the spin crossover transition of ferropericlase, if it exists, is difficult to detect because of the wide pressure range of the transition, which is broadened by the temperature effect and the damping of the amplitude of the slow seismic wave.

Steep energy landscapes and adjustable magnetization states in a four-layer mean-field model with competing interactions

We present a mean-field model with competing interlayer interactions which give rise to organized frustration. The frustration arises due to the difference in modulation length of the interlayer exchange coupling in the mixed-spin state. We calculate the energy landscapes and the equations of state of the system and show how multiple configurations are possible. In addition, the study shows how in such a layered system with competing interactions magnetization jumps can occur at low temperature due to the sharp energy barriers in the landscape. Finally, we examine possible mechanisms of magnetization self-reversal via layer-moment switching.

First-principles insights on the magnetism of cubic SrTi1−xCoxO3−δ

We present hybrid density functional calculations suggesting that magnetism in cubic SrTi1−xCoxO3−δ (STCO) with x = 0.25 is sensitive to the nearest neighbor arrangement of the Co and the presence of oxygen vacancies. Spin polarized calculations for x = 0.25 in which the nearest neighbor (nn) Co spacing is a, 2a or 3a with a the lattice parameter predict lowest energies for the 2a nn separation and favor the ferromagnetic state. Oxygen deficiency (δ=0.125) lowers the average Co valence state and favors mixed valence and spin states (high spin for the Co adjacent to the vacancy and low for the non-adjacent Co), an increase of the band gap and an expansion of the lattice parameter compared to stoichiometric STCO in which both Co ions are low spin. Predicted configurations of the two neighboring Co ions are (t2g5eg0, t2g5eg0) and (t2g4eg2, t2g6eg0) with average 1.0 and 1.6 μB/Co for stoichiometric and 1-O-vacancy systems, respectively.

Rashba spin-orbit-coupled atomic Fermi gases

We investigate theoretically BEC-BCS crossover physics in the presence of Rashba spin-orbit coupling in a system of a two-component Fermi gas with and without a Zeeman field that breaks the population balance between the two components. A bound state (Rashba pair) emerges because of the spin-orbit interaction. We study the properties of Rashba pairs using standard pair fluctuation theory. At zero temperature, the Rashba pairs condense into a macroscopic mixed-spin state. We discuss in detail the experimental signatures for observing the condensation of Rashba pairs by calculating various physical observables which characterize the properties of the system and can be measured in experiment.

Effects of spin transition on diffusion of Fe2+in ferropericlase in Earth's lower mantle

Knowledge of Fe composition in lower-mantle minerals (primarily perovskite and ferropericlase) is essential to a complete understanding of the Earth’s interior. Fe cation diffusion potentially controls many aspects of the distribution of Fe in the Earth’s lower mantle, including mixing of chemical heterogeneities, element partitioning, and the extent of core-mantle communications. Fe in ferropericlase has been shown to undergo a spin transition starting at about 40 GPa and exists in a mixture of high-spin and low-spin states over a wide range of pressures. Present experimental data on Fe transport in ferropericlase is limited to pressures below 35 GPa and provides little information on the pressure dependence of the activation volume and none on the impact of the spin transition on diffusion. Therefore, known experimental data on Fe diffusion cannot be reliably extrapolated to predict diffusion throughout the lower mantle. Here, first-principles and statistical modeling are combined to predict diffusion of Fe in ferropericlase over the entire lower mantle, including the effects of the Fe spin transition. A thorough statistical thermodynamic treatment is given to fully incorporate the coexistence of high- and low-spin Fe in the model of overall Fe diffusion in the lower mantle. Pure low-spin Fe diffuses approximately 10 4 times slower than high-spin Fe in ferropericlase but Fe diffusion of the mixed-spin state is only about 10 times slower than that of high-spin Fe. The predicted Fe diffusivities demonstrate that ferropericlase is unlikely to be rate limiting in transporting Fe in deep earth since much slower Fe diffusion in perovskite is predicted.

Eukaryotic extracellular catalase–peroxidase from Magnaporthe grisea – Biophysical/chemical characterization of the first representative from a novel phytopathogenic KatG group

All phytopathogenic fungi have two catalase–peroxidase paralogues located either intracellularly (KatG1) or extracellularly (KatG2). Here, for the first time a secreted bifunctional, homodimeric catalase–peroxidase (KatG2 from the rice blast fungus Magnaporthe grisea) has been produced heterologously with almost 100% heme occupancy and comprehensively investigated by using a broad set of methods including UV–Vis, ECD and resonance Raman spectroscopy (RR), thin-layer spectroelectrochemistry, mass spectrometry, steady-state & presteady-state spectroscopy. RR spectroscopy reveals that MagKatG2 shows a unique mixed-spin state, non-planar heme b, and a proximal histidine with pronounced imidazolate character. At pH 7.0 and 25 °C, the standard reduction potential E°′ of the Fe(III)/Fe(II) couple for the high-spin native protein was found to fall in the range typical for the KatG family. Binding of cyanide was relatively slow at pH 7.0 and 25 °C and with a Kd value significantly higher than for the intracellular counterpart. Demonstrated by mass spectrometry MagKatG2 has the typical Trp118-Tyr251-Met277 adduct that is essential for its predominantly catalase activity at the unique acidic pH optimum. In addition, MagKatG2 acts as a versatile peroxidase using both one- and two-electron donors. Based on these data, structure–function relationships of extracellular eukaryotic KatGs are discussed with respect to intracellular KatGs and possible role(s) in host–pathogen interaction.

Precision polarization measurements of atoms in a far-off-resonance optical dipole trap

Precision measurement of atomic and nuclear polarization is an essential step for beta-asymmetry measurement of radioactive atoms. In this paper, we report the polarization measurement of Rb atoms in an yttrium-aluminum-garnet (YAG) far-off-resonance optical dipole trap. We have prepared a cold cloud of polarized Rb atoms in the YAG dipole trap by optical pumping and achieved an initial nuclear polarization of up to 97.2(5)$%$. The initial atom distribution in different Zeeman levels is measured by using a combination of microwave excitation, laser pushing, and atomic retrap techniques. The nuclear-spin polarization is further purified to 99.2(2)$%$ in 10 s and maintained above 99$%$ because the two-body collision loss rate between atoms in mixed spin states is greater than the one-body trap loss rate. Systematic effects on the nuclear polarization, including the off-resonance Raman scattering, magnetic field gradient, and background gas collisions, are discussed.

Stern-Gerlach dynamics with quantum propagators

We study the quantum dynamics of a nonrelativistic neutral particle with spin in inhomogeneous external magnetic fields. We first consider fields with one-dimensional inhomogeneities, both unphysical and physical, and construct the corresponding analytic propagators. We then consider fields with two-dimensional inhomogeneities and develop an appropriate numerical propagation method. We propagate initial states exhibiting different degrees of space localization and various initial spin configurations, including both pure and mixed spin states. We study the evolution of their spin densities and identify characteristic features of spin density dynamics, such as the spatial separation of spin components, and spin localization or accumulation. We compare our approach and our results with the coverage of the Stern-Gerlach effect in the literature, and we focus on nonstandard Stern-Gerlach outcomes, such as radial separation, spin focusing, spin oscillation, and spin flipping.

Two dinuclear iron(ii) complexes K[Fe2(L1)(SCN)4]·2(C3H8O) and [Fe2(L1)(SeCN)3(C5H5N)]·H2O are stabilised in the ‘[HS–LS]’ state by a bis-tetradentate pyrazolate-based ligand

Two air-sensitive dinuclear iron(II) complexes, K[Fe(II)(2)(L(1))(SCN)(4)]·2(C(3)H(8)O) (1) and [Fe(II)(2)(L(1))(SeCN)(3)(C(5)H(5)N)]·H(2)O (2), of 3,5-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-1H-pyrazolate [(L(1))(-)] have been prepared. Interestingly, complex 1 is anionic, featuring four coordinated SCN(-) anions and a potassium counterion whereas complex 2 is neutral, containing a coordinated pyridine molecule and only three coordinated SeCN(-) anions. These are the first iron complexes reported for this type of ligand. Magnetic measurements and Mössbauer spectra show that both 1 and 2 are in a '[HS-LS]' mixed spin state between 300 and 2 K.

Variable-temperature, variable-field magnetic circular dichroism spectroscopic study of NifEN-bound precursor and “FeMoco”

NifEN plays a key role in the biosynthesis of the iron–molybdenum cofactor (FeMoco) of nitrogenase. A scaffold protein that hosts the conversion of a FeMoco precursor to a mature cofactor, NifEN can assume three conformations during the process of FeMoco maturation. One, designated ΔnifB NifEN, contains only two permanent [Fe4S4]-like clusters. The second, designated NifENPrecursor, contains the permanent clusters and a precursor form of FeMoco. The third, designated NifEN“FeMoco”, contains the permanent [Fe4S4]-like clusters and a fully complemented, “FeMoco”-like structure. Here, we report a variable-temperature, variable-field magnetic circular dichroism spectroscopic investigation of the electronic structure of the metal clusters in the three forms of dithionite-reduced NifEN. Our data indicate that the permanent [Fe4S4]-like clusters are structurally and electronically conserved in all three NifEN species and exhibit spectral features of classic [Fe4S4]+ clusters; however, they are present in a mixed spin state with a small contribution from the S > ½ spin state. Our results also suggest that both the precursor and “FeMoco” have a conserved Fe/S electronic structure that is similar to the electronic structure of FeMoco in the MoFe protein, and that the “FeMoco” in NifEN“FeMoco” exists, predominantly, in an S = 3/2 spin state with spectral parameters identical to those of FeMoco in the MoFe protein. These observations provide strong support to the outcome of our previous EPR and X-ray absorption spectroscopy/extended X-ray absorption fine structure analysis of the three NifEN species while providing significant new insights into the unique electronic properties of the precursor and “FeMoco” in NifEN.