Experimental Magnetic Susceptibility Research Articles

Structure and physical properties of modified Ti2MnAl compound – Ti2Fe0.5Cr0.5Al and Ti2MnAl0.5In0.5 case

Ti2MnAl was believed to be Spin Gapless Semiconducting (SGS) material, but this state can be achieved only in an inverted variant of Heusler structure. This specific structure is not realized under normal conditions, however, earlier reports suggest that substituting Al by In or Sn should make it possible. This was the motivation for studying the structural and physical properties of Ti2MnAl0.5In0.5 alloy in this paper. We also studied isoelectronic Ti2Fe0.5Cr0.5Al material, as it is well known that properties of Heusler compounds strongly depend on the valence electron count. We report a combined experimental and theoretical study, where we synthesized substituted variants and measured their diffraction patterns. Additionally we performed ab initio calculations using several methods to study the stability of the resulting compounds. We also examined the impact of disorder within Coherent Potential Approximation. Experimental XPS (X-ray Photoemission Spectroscopy) spectra, magnetic susceptibility and electrical resistivity are also discussed.

Lipoic Acid-Functionalized Hexanuclear Manganese(III) Nanomagnets Suitable for Surface Grafting.

Highly anisotropic single-molecule magnets (SMMs) have attracted much interest in the field of molecular magnetism because of their spin features and potential technological applications. Additionally, a great effort has been devoted to the functionalization of such molecule-based systems which are made with ligands containing functional groups suitable to connect SMMs to junction devices or to perform their grafting on surfaces of different substrates. We have synthesized and characterized two lipoic acid-functionalized and oxime-based Mn(III) compounds, of formula [Mn6(μ3-O)2(H2N-sao)6(lip)2(MeOH)6][Mn6(μ3-O)2(H2N-sao)6(cnph)2(MeOH)6]}·10MeOH (1) and [Mn6(μ3-O)2(H2N-sao)6(lip)2(EtOH)6]·EtOH·2H2O (2) [H2N-saoH2 = salicylamidoxime, lip = lipoate anion, cnph = 2-cyanophenolate anion]. Compound 1 crystallizes in the space group Pī of the triclinic system and 2 crystallizes in the space group C2/c of the monoclinic system. In the crystal, neighboring Mn6 entities are linked using non-coordinating solvent molecules, which are H-bonded to N atoms of -NH2 groups of amidoxime ligand. In addition, Hirshfeld surfaces of 1 and 2 were calculated to study the variety of intermolecular interactions and the different levels of importance that take place in their crystal lattice; this type of computed study is the first time performed on Mn6 complexes. The study of the magnetic properties of 1 and 2 through dc magnetic susceptibility measurements reveals the coexistence of ferromagnetic and antiferromagnetic exchange couplings between the Mn(III) metal ions in both compounds, the latter being the predominant magnetic interaction. A spin S = 4 value of the ground state was obtained using isotropic simulations of the experimental magnetic susceptibility data for both 1 and 2. Ac magnetic susceptibility measurements show features typical of slow relaxation of the magnetization in 1 and 2, which indicate that SMM behavior takes place in both compounds.

Unconventional dual 1D\u20132D quantum spin liquid revealed by ab initio studies on organic solids family

Organic solids host various electronic phases. Especially, a milestone compound of organic solid, beta ^{prime}-X[Pd(dmit)2]2 with X=EtMe3Sb shows quantum spin-liquid (QSL) properties suggesting a novel state of matter. However, the nature of the QSL has been largely unknown. Here, we computationally study five compounds comprehensively with different X using 2D ab initio Hamiltonians and correctly reproduce the experimental phase diagram with antiferromagnetic order for X=Me4P, Me4As, Me4Sb, Et2Me2As and a QSL for X=EtMe3Sb without adjustable parameters. We find that the QSL for X=EtMe3Sb exhibits 1D nature characterized by algebraic decay of spin correlation along one direction, while exponential decay in the other direction, indicating dimensional reduction from 2D to 1D. The 1D nature indeed accounts for the experimental specific heat, thermal conductivity and magnetic susceptibility. The identified QSL, however, preserves 2D nature as well consistently with spin fractionalization into spinon with Dirac-like gapless excitations and reveals duality bridging the 1D and 2D QSLs.

Interpretation of the magnetic susceptibility behaviour of soft carbon steels based on the scaling theory of second order phase transitions for systems with supercritical disorder

The experimental magnetic susceptibility curves of several soft steel grades, like interstitial free (IF) or low carbon (LC) steels, can be interpreted within the framework of universal scaling functions obtained for systems with quenched disorder, such as the one described by the random field Ising model with supercritical disorder. Mean-field theory (both scalar and site-dependent) is used to explore the behaviour at the proximity of the coercive field, and explicit expressions are derived. As a result, the susceptibility values close to the coercive field can be approximated to a good extend by a Lorentzian function. Theoretical results are compared against a number of experimental curves obtained from interstitial free (IF) and extra low carbon (ELC) steels subjected to isothermal annealing.

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Cuprates phase diagram deduced from magnetic susceptibility: What is the ‘true’ pseudogap line?

Two contradictory phase diagrams have dominated the literature of high-Tc cuprate superconductors. Does the pseudogap line cross the superconducting Tc-dome or not? To answer, we have revisited the experimental magnetic susceptibility and knight shift of four different compounds, La1−xSrxCuO4, Bi2Sr2Ca1−xYxCu2O8, Bi2Sr2CaCu2O8+y, YBa2Cu3O6+y, as a function of temperature and doping. The susceptibility can be described by the same function for all materials, having a magnetic and an electronic contributions. The former is the 2D antiferromagnetic (AF) square lattice response, with a characteristic temperature of magnetic correlations Tmax. The latter is the ‘Pauli’ term, revealing the gap opening in the electronic density of states at the pseudogap temperature T∗.From precise fits of the data, we find that Tmax(p) decreases linearly as a function of doping (p) over a wide range, but saturates abruptly in the overdoped regime. Concomitantly, T∗(p) is linear and tangent to the dome, either crossing or approaching Tmax(p) at the top of the dome, indicating a qualitative change of behavior from underdoped to overdoped regimes.Contrary to the idea that the pseudogap terminates just above optimal doping, our analysis suggests that the gap exists throughout the phase diagram. It is consistent with a pseudogap due to hole pairs, or ‘pairons’, above Tc. We conclude that Tmax, reflecting the AF magnetic correlations, has often been misinterpreted as the pseudogap temperature T∗.

Temperature Dependence of 1 H Paramagnetic Chemical Shifts in Actinide Complexes, Beyond Bleaney's Theory: The AnVI O2 2+ -Dipicolinic Acid Complexes (An=Np, Pu) as an Example.

Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1 H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans' method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.

Defect induces effect on LaCoO3: From diamagnetism to ferrimagnetism due to vacancy in the bulk lattice

LaCoO3 suffers spin crossover as a function of temperature, changing from low-spin state to intermediate-state and, at high temperatures, it also changes to a high-spin state. Nano-confinement of this material induces a long-range magnetic ordering, with a critical temperature close to 83 K; and to deepening this debate whether it is a consequence of nanotopology or defects on the surface, we have prepared the compositions of the series La1−x□xCo1−x3+Cox4+O3 (x=0.00, 0.04, 0.08 and 0.12). We experimentally found an axial compression of the CoO6 octahedra, verified by the new elasticity parameter σ; and, based on the Jahn-Teller theorem, we proposed a spin state and a mean-field model, that successfully fitted the experimental magnetic susceptibility. As an output, we found that the Co(III) sub-lattice has an antiparallel intra-lattice alignment; while the Co(IV) sub-lattice has a parallel intra-lattice alignment. As a part of the ferrimagnetic model considered, the net magnetization of both sub-lattices (Co(III) and Co(IV)), are aligned in opposition. The magnetic behavior of these vacant bulk samples is similar to those nanostructured ones, with the same critical temperature, and therefore we claim that the long-range magnetic ordering found for those nanomaterials has its origin on the Jahn-Teller effect on the surface of the sample.

Determination of ligand field splitting in lanthanide(iii) monoporphyrinato complexes.

The 4f-electronic structures of the ground multiplet states of a series of lanthanide(iii) monoporphyrinato complexes with a cyclen as the capping ligand [Ln(TPP)(cyclen)]Cl (Ln = Tb, Dy, Ho, Er, Tm, and Yb; TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4,7,10-tetraazacyclododecane) have been determined using experimental NMR and magnetic susceptibility data. Magnetic susceptibilities of the microcrystalline samples of [Ln(TPP)(cyclen)]Cl were measured in the range of 1.8-300 K. NMR signals corresponding to the protons on the porphyrin ring show marked paramagnetic shifts (lower = Tb, Dy, Ho, and Yb; higher = Er and Tm) in comparison with the diamagnetic Y congener. A set of ligand-field parameters that simultaneously reproduces the magnetic susceptibilities and the paramagnetic shifts has been determined by using a self-developed multidimensional optimization program. In addition, CASSCF calculations were carried out for further insight into their electronic structures.

Molecular Mobility Effect on Magnetic Interactions in All-Organic Paramagnetic Liquid Crystal with Nitroxide Radical as a Hydrogen-Bonding Acceptor.

We synthesized new chiral all-organic liquid crystalline (LC) compounds with nitroxide (NO) and hydroxy (OH) groups, which form intermolecular hydrogen bonds between the NO and OH groups. The LC compounds show hexagonal columnar phases at room temperature, which solidify as LC glasses at low temperature. The experimental magnetic susceptibility of each of the compounds in the LC and isotropic phases is larger than that theoretically estimated on the simple assumption about the amount of the spins, whereas it accords with the theoretical one in the LC glass state. It is called magneto-LC effects. The difference between experimental and theoretical magnetic susceptibilities gradually increases as temperature increases through the LC glass state-to-LC phase transition. It suggests that molecular mobility is one of the origins of the magneto-LC effects.

Theoretical Investigation of Plutonium-Based Single-Molecule Magnets.

The electronic structure of a plutonium-based single-molecule magnet (SMM) was theoretically examined by means of multiconfigurational electronic structure theory calculations, including spin-orbit coupling effects. All Pu 5f to 5f transitions for all possible spin states were computed, as well as ligand to metal charge transfer and Pu 5f to 6d transitions. Spin-orbit coupling effects were included a posteriori to accurately describe the electronic transitions. The spin-orbit coupled energies and magnetic moments were then used to compute the magnetic susceptibility curves. The experimental electronic structure and magnetic susceptibility curve were reproduced well by our calculations. A compound with a modified electron-donating ligand (namely a carbene ligand) was also investigated in an attempt to tune the electronic properties of the plutonium SMM, revealing a higher ligand field splitting of the 5f orbitals of Pu, which could in turn enhance the barrier against magnetic relaxation.

Self-assembly of tetranuclear metallogrid with an asymmetric ligand derived from 2-oxo-quinoline derivative

The current work reports the construction and self-assembly studies of tetranuclear metallogrid molecules [Co4(LOH)4] (1) and [Ni4(LOH)4] (2) from an asymmetric 2-oxo-quinoline donor. Employment of different metals has given rise to different architectures ranging from a head-to-head fashion in complex 1 to head-to-tail arrangement in 2. Within the individual ligand, the protons on all the carbohydrozone and imine groups were lost and H2LOH acted as a dianionic ligand in the complex (denoted as LOH). The single-crystal X-ray diffraction analysis and experimental magnetic susceptibilities indicated the trans-[CoIII–CoII–CoIII–CoII] mixed valence in complex 1. However, the nickel was divalent for all of the four atoms and exhibited weak antiferromagnetic interactions in complex 2.

A Terminal Fluoride Ligand Generates Axial Magnetic Anisotropy in Dysprosium Complexes

AbstractThe first dysprosium complexes with a terminal fluoride ligand are obtained as air‐stable compounds. The strong, highly electrostatic dysprosium–fluoride bond generates a large axial crystal‐field splitting of the J=15/2 ground state, as evidenced by high‐resolution luminescence spectroscopy and correlated with the single‐molecule magnet behavior through experimental magnetic susceptibility data and ab initio calculations.

A Terminal Fluoride Ligand Generates Axial Magnetic Anisotropy in Dysprosium Complexes.

The first dysprosium complexes with a terminal fluoride ligand are obtained as air-stable compounds. The strong, highly electrostatic dysprosium-fluoride bond generates a large axial crystal-field splitting of the J=15/2 ground state, as evidenced by high-resolution luminescence spectroscopy and correlated with the single-molecule magnet behavior through experimental magnetic susceptibility data and ab initio calculations.

Influence of classical anisotropy fields on the properties of Heisenberg antiferromagnets within unified molecular field theory

A comprehensive study of the influence of classical anisotropy fields on the magnetic properties of Heisenberg antiferromagnets within unified molecular field theory versus temperature T, magnetic field H, and anisotropy field parameter hA1 is presented for systems comprised of identical crystallographically-equivalent local moments. The anisotropy field for collinear z-axis antiferromagnetic (AFM) ordering is constructed so that it is aligned in the direction of each ordered and/or field-induced thermal-average moment with a magnitude proportional to the moment, whereas that for XY anisotropy is defined to be in the direction of the projection of the moment onto the xy plane, again with a magnitude proportional to the moment. Properties studied include the zero-field Neel temperature TN, ordered moment, heat capacity and anisotropic magnetic susceptibility of the AFM phase versus T with moments aligned either along the z axis or in the xy plane. Also determined are the high-field magnetization perpendicular to the axis or plane of collinear or planar noncollinear AFM ordering, the high-field magnetization along the z axis of a collinear z-axis AFM, spin-flop (SF), and paramagnetic (PM) phases, and the free energies of these phases versus T, H, and hA1. Phase diagrams at T = 0 in the Hz-hA1 plane and at T > 0 in the Hz-T plane are constructed for spins S = 1/2. For hA1 = 0 the SF phase is stable at low field and the PM phase at high field with no AFM phase present. As hA1 increases, the phase diagram contains the AFM, SF and PM phases. Further increases in hA1 lead to the disappearance of the SF phase and the appearance of a tricritical point on the AFM-PM transition curve. Applications of the theory to extract hA1 from experimental low-field magnetic susceptibility data and high-field magnetization versus field isotherms for single crystals of AFMs are discussed.

Quantum Chemical Characterization of Single Molecule Magnets Based on Uranium

Multiconfigurational electronic structure theory calculations including spin-orbit coupling effects were performed on four uranium-based single-molecule-magnets. Several quartet and doublet states were computed and the energy gaps between spin-orbit states were then used to determine magnetic susceptibility curves. Trends in experimental magnetic susceptibility curves were well reproduced by the calculations, and key factors affecting performance were identified.

Puzzling Lack of Temperature Dependence of the PuO2 Magnetic Susceptibility Explained According to Ab Initio Wave Function Calculations.

The electronic structure and the magnetic properties of solid PuO2 are investigated by wave function theory calculations, using a relativistic complete active space (CAS) approach including spin-orbit coupling. The experimental magnetic susceptibility is well reproduced by calculations for an embedded PuO812- cluster model. The calculations indicate that the surprising lack of temperature dependence of the magnetic susceptibility χ of solid PuO2 can be rationalized based on the properties of a single Pu4+ ion in the cubic ligand field of the surrounding oxygen ions. Below ∼300 K, the only populated state is the nonmagnetic ground state, leading to standard temperature-independent paramagnetism (TIP). Above 300 K, there is an almost perfect cancellation of temperature-dependent contributions to χ that depends delicately on the mixing of ion levels in the electronic states, their relative energies, and the magnetic coupling between them.

An investigation by DFT of the electronic structure and magnetic properties of a novel μ-oxo-iron(III) complex with the 1,10-phenathroline ligand

The crystal structure of (H-phen)2[Fe2(μ-O)(H2O)6(phen)2](NO3)6 has been determined using single-crystal X-ray crystallography at low and room temperature. Complex 1 crystallizes in the monoclinic C2/c space group. This compound contained two iron(III) centers which are bridged by one oxygen atom to form dinuclear units. This binuclear complex exhibits strong antiferromagnetic coupling between the two iron(III) centers with g=2, S=5/2 and J=−223cm−1. An investigation of the magnetic order was performed using spin projected broken symmetry via density functional theory. This approach of broken symmetry (BS) has provided a good numerical estimation of the J value (J=−198cm−1), which is in agreement with the experimental magnetic susceptibility measurements. By means of DFT and TD-DFT methods, the electronic absorption and infrared spectra of the title compound were predicted with good agreement with the experimental data. Natural bond orbital (NBO) analysis has been used to explain the formation of a hydrogen bond and the most possible interaction. In addition, the chemical reactivity of the complex has been obtained by mapping electron density with molecular electrostatic potential (MEP) and the electrical, optical and chemical properties have been investigated through the energies of the frontier molecular orbitals (FMO).

Synthesis, structures, and magnetic properties of two closely-related manganese(II) coordination polymers

The reactions of Mn2+ ion with 4-nitrobenzene-1,2-bicarboxylic acid in the presence of bipyridyl-type coligands gave two new manganese(II) coordination polymers, [Mn2(Nbdc)2(Bipyp)(H2O)4] n (I) and [Mn2(Nbdc)2(Bipye)(H2O)4] n (II) (H2Nbdc = 4-nitrobenzene-1,2-bicarboxylic acid, Bipyp = 1,3-bi(4-pyridyl)propane, and Bipye = 1,2-bi(4-pyridyl)ethane). Both two complexes contain uniform carboxyl-bridged manganese chains with the composition of [Mn2(Nbdc)2(H2O)4] n , which are interlinked by interchain Bipyp/Bipye spacers to afford two closely-related layers (CIF files CCDC nos. 1008182 (I) and 1008183 (II)). Magnetic studies for two compounds show the presence of similar antiferromagnetic couplings between the adjacent Mn2+ ions through the carboxyl bridges, the best fittings to the experimental magnetic susceptibilities gave J =–0.20 cm–1 and g = 1.96 for I, and J =–0.24 cm–1 and g = 1.98 for II. Similar magnetic parameters and thermal behaviors further verify that two compounds possess closely-related structures.

Hybridization and spin-orbit coupling effects in the quasi-one-dimensional spin-12magnetBa3Cu3Sc4O12

We study electronic and magnetic properties of the quasi-one-dimensional spin-1/2 magnet Ba3Cu3Sc4O12 with a distinct orthogonal connectivity of CuO4 plaquettes. An effective low-energy model taking into account spin-orbit coupling was constructed by means of first-principles calculations. On this basis a complete microscopic magnetic model of Ba3Cu3Sc4O12, including symmetric and antisymmetric anisotropic exchange interactions, is derived. The anisotropic exchanges are obtained from a distinct first-principles numerical scheme combining, on one hand, the local density approximation taking into account spin-orbit coupling, and, on the other hand, projection procedure along with the microscopic theory by Toru Moriya. The resulting tensors of the symmetric anisotropy favor collinear magnetic order along the structural chains with the leading ferromagnetic coupling J1 = -9.88 meV. The interchain interactions J8 = 0.21 meV and J5 = 0.093 meV are antiferromagnetic. Quantum Monte Carlo simulations demonstrated that the proposed model reproduces the experimental Neel temperature, magnetization and magnetic susceptibility data. The modeling of neutron diffraction data reveals an important role of the covalent Cu-O bonding in Ba3Cu3Sc4O12.