Anomalous dependence of the magnetic resonance signal of cesium atoms in the afterglow in an N<Subscript>2</Subscript>-Ar mixture

The investigation of spin-exchange collisions between optically oriented cesium atoms in the ground ² S _1/2 state and nitrogen atoms in the ground ⁴ S _3/2 state reveals an anomalous behavior of the magnetic resonance signal of cesium atoms in the afterglow in an N₂-Ar mixture, namely, the magnetic resonance signal is slowly enhanced during the time interval between the high-frequency pulses exciting a discharge in the absorption cell. It is found that such a behavior of the magnetic resonance signal is explained by a slow change in the concentration of nitrogen atoms in the absorption cell, which affects the magnetic resonance of cesium atoms via efficient spin exchange.     

Covalence-induced stabilization of an intermediate-spin state and the magnetic susceptibility of LaCoO<Subscript>3</Subscript>

The energies of terms with spins S = 0, 1, 2 have been found using exact diagnoalization of the multielectron Hamiltonian of a multiband pd model for the CoO₆ cluster. Co (e _g orbital)-O hops, which form the covalent σ bond, are shown to decrease the energy of the state (IS) with an intermediate spin (S = 1) as compared to the energy of the state (LS) with a low spin (S = 0). An analogue of the Tanabe-Sugano diagram that takes into account the covalence of the CoO₆ cluster is constructed. The state with S = 1 is shown to be a ground state at certain model parameters. An increase in temperature is established to decrease the crystal field and, thus, favors the transition of the ground state from LS to IS at T = 100 K and the transition of the IS ground state to a state (HS) with a high spin (S = 2) at T = 550 K. The magnetic susceptibility of LaCoO₃ is calculated with allowance for the LS, IS, and HS states and for the fact that the HS state exhibits threefold orbital degeneracy of the t _2g shell, which results in an effective orbital moment L = 1 and the importance of spin-orbit interaction. The behavior of this magnetic susceptibility agrees well with the experimental x(T) dependence of LaCoO₃.     

High-pressure effects on the crystal and magnetic structure of the Nd0.78Ba0.22CoO3 cobaltite

The crystal and magnetic structure of the Nd_0.78Ba_0.22CoO₃ cobaltite is studied by neutron diffraction at high pressures up to 4.2 GPa in the temperature range 10–300 K. The pressure dependences of structural parameters are obtained. Ferromagnetic ordering of the Co sublattice is observed at normal pressure below T _C ～ 140 K, and ferrimagnetic ordering of the Co and Nd sublattices with an antiparallel direction of magnetic moments appears at T _F ～ 40 K. The magnetic moment of Co and the temperature T _C change slightly under pressure, which points to the stability of the initial intermediate-spin (S = 1) state of Co³⁺ ions. This behavior differs considerably from the characteristic behavior of cobaltites that are close in chemical composition and structure and exhibit ferromagnetic ordering of only the Co sublattice. In these cobaltites, the magnetic moment of Co is substantially suppressed and T _C decreases under pressure, which is related to the change in the state of Co³⁺ ions from the intermediate spin state to the nonmagnetic low-spin state (S = 0). The interplay between the appearance of the magnetic interaction of the R-Co sublattices and the stability of the spin state of Co³⁺ ions in the Nd_0.78Ba_0.22CoO₃ cobaltite is discussed.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Effect of Dzyaloshinskii−Moriya interactions on Kagome anti-ferromagnetic clusters

The low energy and low temperature behavior of a few finite size Kagome clusters, including mixed spin systems of S=1/2 and S=1, with the nearest neighbor Heisenberg antiferromagnetic model is studied under the influence of out-of-plane Dzyaloshinskii?Moriya interactions (DMI) within the exact diagonalization formalism. The ground state of all the finite size systems is found to be present in the lowest spin sector with a finite gap to the lowest magnetic excitation irrespective of the strength of out-of-plane DMI. The energy level structures within the non-magnetic ground state and the lowest magnetic state have been studied for all the systems as a function of DMI. The characteristic signature of such low-lying non-magnetic excitations is reflected in the low temperature behavior of the specific heat. It is also found that the ground state chiral structure (characterized by the vector chiral order of the system) in the xy-plane shows sharp changes as a function of out-of-plane DMI at level crossing or avoided crossing regions. The in-plane spin ordering for each system is also studied with the estimation of static structure factor as a response to the varying strength of DMI.     

Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS₂. Measurements have been carried out to ascertain the spin state of Fe³⁺ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using aS=1/2 spin ground state for the Fe³⁺ ion. The features in the optical spectra have been assigned to transitions within thed-electron manifold of the Fe³⁺ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at ∼565K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state atT _N=250 K. The intra and interchain exchange constants,J andJ′, have been evaluated from the experimental susceptibilities using the relationship between these quantities, andχ _max,T _max, andT _N for a spin 1/2 one-dimensional chain. The values areJ=−440.71 K, andJ′=53.94 K. Using these values ofJ andJ′, the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used belowT _N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infiniteS=1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS₂. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75×10⁻⁴ emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7×10⁻⁴ emu/mol) obtained from the experimental data.     

Low temperature specific heat of bi-layered manganites La2−2xSr1+2xMn2O7 (x=0.3 and 0.5)

The specific heat (C) of bi-layered manganites La_2−2xSr_1+2xMn₂O₇ (x=0.3 and 0.5) is investigated for the ground state of low temperature excitations. A T^3/2 dependent term in the low temperature specific heat (LTSH) is identified at zero magnetic field and suppressed by magnetic fields for x=0.3 sample, which is consistent with a ferromagnetic metallic ground state. For x=0.5 sample, a T² term is observed and is consistent with a two-dimensional (2D) antiferromagnetic insulator. However, it is almost independent of magnetic field within the range of measured temperature (0.6-10 K) and magnetic field (6 T).     

Spin crossover in the magnetic phase transition in YBa2(Cu1−x Fex)3O7±δ superconductors

All iron ions in the Cu1 and Cu2 local lattice sites of the YBa₂(Cu_0.9 ⁵⁷Fe_0.1)₃O_7.01 superconductor with T _c=31 K experienced magnetic ordering below T _m=22 K. Therefore, at T < T _m, magnetic ordering coexisted with superconductivity. According to the Mössbauer spectroscopy data, iron ions in Cu2 (Fe2) sites were in the low-spin state at T < T _m(S= 3/2 or 1/2), whereas an equal number of iron ions in Cu1 (Fe1) sites were in the high-spin Fe³⁺ state (S=5/2). The magnetic transition near T _m changed iron ion spin states-low-spin ions turned into high-spin ions, and vice versa. This preserved the spin balance between iron ions in the Cu1 and Cu2 layers. Control measurements on other samples of the YBa₂(Cu_{1? x} Fe_x)₃O_7±δ series substantiated these conclusions.     

Proton dynamics in antiferroelectric CsH3(SeO3)2 single crystal investigated by 1H NMR measurements

¹H nuclear magnetic resonance (NMR) measurements have been performed to study the proton dynamics associated with the antiferroelectric transition of a hydrogen-bonded single crystal of CsH₃(SeO₃)₂. Herein, ¹H NMR spectrum, shift, linewidth, and spin-lattice relaxation rate 1/T₁ are measured in the temperature range of 80–296 K with the c-axis parallel to a magnetic field of ~4.85 T. The spectrum exhibits a composite structure with two narrow peaks at 296 K; at a low temperature, this structure evolves into a single broad shape with three humps. This complex shape and evolution are deconvoluted into five or six components based on the number of inequivalent and disordered hydrogen sites. By estimating the chemical shift and linewidth for each proton site, we identify all peaks. The spin-lattice relaxation recovery exhibits a double-exponential behavior with two relaxation times, short T_1S and extremely large T_1L. Both T_1S and T_1L follow Arrhenius behavior. From the respective 1/T₁(T), the activation energies for proton motion are measured to be small: 1.16 ± 0.1 and 0.83 ± 0.06 kJ/mol for T_1S and T_1L, respectively. While the static NMR data, chemical shift and linewidth, show no evidence for the transition, the dynamic data 1/T_1L highlights a clear increase across T_N = 145 K, which is possibly a signature of the transition.     

Spin conversion detected by Mössbauer spectroscopy and μSR on a 1D FeII paramagnetic chain

While magnetic properties of the 1D chain [Fe(hyetrz)₃](4-bromophenylsulfonate)₂ investigated over the temperature range from 300 K to 2 K show paramagnetic behavior, detailed ⁵⁷Fe Mössbauer and muon spin relaxation measurements reveal an unexpected spin conversion. Approximately ~14 % of the high-spin ions are found to convert to the low-spin state with a transition temperature T _1/2?~?120 K.     

NMR studies of magnetic superconductor RuSr2RECu2O8 (RE=Gd, Eu and Y)

We have carried out ^99/101Ru and ^63/65Cu nuclear magnetic resonance experiments in order to investigate magnetic and electronic properties of the magnetic superconductor RuSr₂RECu₂O₈ (RE=Gd, Eu and Y). The two kinds of ^99/101Ru signals were observed in the magnetically ordered state for each system, suggesting a charge segregation of Ru⁵⁺ (S=3/2) and Ru⁴⁺ (S=1) ions in the RuO₂ layers. The internal field at the Cu sites is revealed to be of the order of kilo Oe, indicating weak magnetic interactions between the CuO₂ and RuO₂ planes. The temperature dependence of nuclear spin-lattice relaxation time T₁ of ⁶³Cu in RE=Y shows a ‘spin gap’ like behavior, suggesting the system is under-doped.     

Mössbauer spectroscopic studies of spin crossover in tris(N, N′-dialkyldithiocarbamato) iron (III) complexes: effect of alkyl substituents

Spin crossover behavior in tris(N,N′-dialkyldithiocarbamato) iron(III) complexes with varying alkyl groups has been studied by variable temperature magnetic moment and Mössbauer spectral studies. All the complexes may be divided into three broad groups; high spin (μ _eff > 4.8 BM), intermediate spin (μ _eff?=?3.5???4.6 BM) and low spin (μ _eff?< 3.2 B.M). Room temperature (RT) Mössbauer spectra exhibit an asymmetric doublet resolved into two doublets corresponding to high and low spin states. Estimated % contributions of HS and LS states and calculated μ _eff were comparable with the experimentally determined values. It has been shown that some complexes undergo spin crossover, ⁶A₁g→²T₂g whereas others exhibit spin transitions ⁶A₁g →⁴T₁g or ⁴T₁g → ²T₂g. IR spectra show characteristic ν _(Fe???S) bands in the region 208–285 (HS) and 311–380 cm^???1 (LS). Nature of alkyl groups affects the spin state.     

Mössbauer study of 1/8 anomaly in La2−x Ba x CuO4

The measurements of Mössbauer effect, magnetic susceptibility and muon spin relaxation have been carried out for the high-T _c superconductor La_2?x Ba _x CuO₄. The intensity of Mössbauer doublet spectrum of the sample of x～1/8 begins to decrease rapidly at a certain temperature T _m, which we define as a magnetic transition temperature T _Möss. This temperature almost agrees with T _μSR determined from muon spin relaxation. The quadrupole doublet disappears at low temperature below T _m but a clearly splitted spectrum is not observed even at 4.2 K, which indicates a peculiar magnetic state with a wide distribution of internal magnetic field. Around x～1/8, the superconducting critical temperature T _c and T _m are competed each other. In conclusion, superconductivity disappears around 1/8 hole concentration and a peculiar magnetic state such as spin density wave appears.     

Proton spin relaxation in hexagonal ice

Measurements of the rotating frame proton spin relaxation timeT _1p in hexagonal ice single crystals as a function of temperature ? for various rotating magnetic field strengths reveal the expectedT _1p minimum at the lowest practicable field values. This allows a very precise determination of the proton correlation (? molecular jump) time τ_c and the related activation energy ΔE by means of the theoretical reasoning of relaxation spectroscopy. We find the Arrhenius-law temperature dependenceτ _c=1.99×10^?17exp(0.603/8.61×10^?5 ?)sec, which is in good agreement with our earlier indirect derivation.     

Terahertz Cyclotron Photoconductivity in a Highly Unbalanced Two-Dimensional Electron–Hole System

The magnetic properties of the α-Fe₂O₃ hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0–72 GPa and the temperature range of 36–300 K in order to study the magnetic properties at a phase transition near a critical pressure of ~50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0–77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of ~48 GPa. This state is probably related to the spin crossover in Fe³⁺ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS–LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe³⁺ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P–T phase diagram of α-Fe₂O₃ at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.     

Effect of Ta<Superscript>5+</Superscript> substitution for Mn on the ground state of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>

We report the charge state modification effects at the Mn site on the ground state properties of colossal magnetoresistive manganites. Ta⁵⁺ substitution results in an appreciable increase in the lattice parameters and unit cell volume due to increased Mn³⁺ concentration. The ferromagnetic-metallic ground state modifies to a cluster glass insulator for . The reduction in the transition temperatures with increasing x is ∼39 K/at.%. Besides the modification of majority carrier concentration due to increased Mn³⁺ concentration and enhanced local structural effects, the local electrostatic potential of the substituent seems to contribute to the unusually strong reduction of the transition temperatures of the compounds. Thermo magnetic irreversibility just below Curie temperature (T_c), non-saturation of magnetization, two distinct magnetic transitions in ac susceptibility in an appropriate static field: close to T_c and other at low temperature (the spin freezing temperature (T_g)) and non-stationary dynamics with a characteristic maximum in the magnetic viscosity close to T_g confirm a cluster glass state for . These results find additional support from a linear low temperature magnetic specific heat of x = 0.10 with a characteristic broad maximum close to T_g.     

Features of the Formation of the Spin Polarization of an Alkali Metal at the Resolution of Hyperfine Sublevels in the <Superscript>2</Superscript><Emphasis Type="Italic">S</Emphasis><Subscript>1/2</Subscript> State

The optical orientation of the angular momenta of alkali atoms in the presence of a buffer gas (molecular nitrogen) has been studied experimentally. It has been shown that, even at a low concentration of molecular nitrogen in the cell, the excitation of ¹³³Cs atoms from the lower hyperfine level with F = 3, which belongs to the ground ²S_1/2 state, results in a larger amplitude of the magnetic resonance than the excitation from the hyperfine level with F = 4. This result has been theoretically explained under the assumption that the spin state of the alkali atomic nucleus does not change at collision with a nitrogen molecule, which is accompanied by a nonradiative transition of the alkali atom from the excited ²P_1/2 state to the ground ²S_1/2 state.     

NMR study on the quasi one-dimensional quantum spin magnet with ladder structure

The two-legged spin ladder Cu(CO₃)_0.5(ClO₄)(H₂O)_0.5(NH₃)_2.5 consists of a rung formed by two Cu(II)’s and of a spacing molecule CO\(_{3}^{2-}\) between each two rungs. The non-centrosymmetric shape of CO\(_{3}^{2-}\) molecule brings a slight bond alternation along the leg, and hence the system can be considered as an alternating spin chain, which is confirmed so far by the temperature dependence of magnetic susceptibility. In order to investigate its spin state at low temperatures, we have performed experiments of ¹H-NMR, magnetization and specific heat under wide range of magnetic field, and have found the critical diverging of longitudinal relaxation rate 1/T ₁, the spectral broadening and the lambda-type anomaly in specific heat at T _N? 3.4 K, indicating the existence of long range magnetic order. In paramagnetic state well above T _N, 1/T ₁ showed a power-law temperature dependence, suggesting the realization of Tomonaga Luttinger liquid state.     

Temperature dependence of the hyperfine parameters of a natural orthopyroxene Fe0.87Mg0.13SiO3

The Mössbauer parameters of an iron rich orthopyroxene Fe_xMg_1−xSiO₃ with x = 0.87 (natural compound named XYZ) have been analyzed in detail as a function of temperature in the paramagnetic and in the magnetic region. The magnetic ordering temperature obtained by Mössbauer spectroscopy is T_N = 27 ± 1 K. Above T_N, a quite different behaviour of the quadrupole interactions of the Fe²⁺ in the M1 and M2 sites has been observed as a function of temperature. It can be explained by the different energy splittings of the orbital states of the ⁵T₂ ground state of high spin iron (II). Below T_N, using simple level scheme considerations related to the low symmetry of the Fe²⁺ oxygen octahedra, one can assign unambiguously the values o of the hyperfine fields to Fe²⁺ in M1 and M2. In this low temperature range the Mössbauer spectra can be accounted for by a distribution of hyperfine fields P(H_h.f(M1)) and P(H_h.f(M2)) related to the various Fe²⁺-Mg²⁺ nearest neighbour configurations surrounding the Fe²⁺ probe located on the M1 or M2 site.     

Charge density wave transition in Na2Ti2Sb2O probed by 23Na NMR

Herein we investigated the electronic properties of layered transition-metal oxides Na2Ti2Sb2O by23Na nuclear magnetic resonance(NMR)measurement.The resistivity,susceptibility and specific heat measurements show a phase transition at approximately 114 K(TA).No splitting or broadening in the central line of23Na NMR spectra is observed below and above the transition temperature indicating no internal field being detected.The spin-lattice relaxation rate divided by T(1/T1T)shows a sharp drop at about 110 K which suggests a gap opening behavior.Below the phase transition temperature zone,1/T1T shows Fermi liquid behavior but with much smaller value indicating the loss of large part of electronic density of states(DOS)because of the gap.No signature of the enhancement of spin fluctuations or magnetic order is found with the decreasing temperature.These results suggest a commensurate charge-density-wave(CDW)phase transition occurring.