Structures,energetics and magnetic properties of (NiSn)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> clusters with <Emphasis Type="Italic">n</Emphasis> = 1–6

We report the results of calculations which were performed to investigate equilibrium structures, electronic and magnetic properties of stoichiometric (NiSn) _n clusters with n = 1–6 within the framework of density functional theory. The calculated results show that the structural arrangement of (NiSn) _n clusters is dominated by the Ni-Sn and Ni-Ni interactions. We find that these binary clusters show significant variation in the geometries as compared to that of the host nickel clusters. The preference for tetrahedron unit of Ni₃Sn is seen in the lowest-energy configuration of these clusters. The multi-centre bonding between Ni atoms play an important role in stabilizing the stoichiometric Ni-Sn clusters. Doping of Sn atoms enhances the binding energy and reduces the ionization potential of nickel clusters. These binary clusters prefer the lowest spin state. For (NiSn)₆ the magnetic moment is 0 μB. The complete quenching of the cluster magnetic moment appears to be due to the antiferromagnetic alignment of atomic spins as revealed by the spin density plots.     

Magnetic properties of the tetranitrosyl-iron complex Fe<Subscript>2</Subscript>(SC<Subscript>3</Subscript>H<Subscript>5</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>(NO)<Subscript>4</Subscript>

The magnetic properties of the binuclear nitrosyl-iron complexes Fe₂(SC₃H₅N₂)₂(NO)₄ are investigated. It is demonstrated that several types of particles, such as dimers with a pair of spins 1/2, dimers with a pair of spins 5/2, and paramagnetic particles with spin 3/2, make a contribution to the magnetic properties of the complexes. A decrease in the temperature below 25 K leads to a change in the shape of the EPR spectra corresponding to these dimers, so that Lorentzian lines (homogeneous broadening) transform into Gaussian lines (inhomogeneous broadening). This is accompanied by a stepwise change in the EPR line width and g factors. The change in the line shape indicates that complexes become asymmetric at low temperatures, possibly, due to the decrease in the spin exchange frequency below the frequency of the microwave field of the spectrometer.     

Magnetic state of the structural separated anion-deficient La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>MnO<Subscript>2.85</Subscript> manganite

The results of neutron diffraction studies of the La_0.70Sr_0.30MnO_2.85 compound and its behavior in an external magnetic field are stated. It is established that in the 4–300 K temperature range, two structural perovskite phases coexist in the sample, which differ in symmetry (groups R[`3]cR\bar 3c and I4/mcm). The reason for the phase separation is the clustering of oxygen vacancies. The temperature (4–300 K) and field (0–140 kOe) dependences of the specific magnetic moment are measured. It is found that in zero external field, the magnetic state of La_0.70Sr_0.30MnO_2.85 is a cluster spin glass, which is the result of frustration of Mn³⁺-O-Mn³⁺ exchange interactions. An increase in external magnetic field up to 10 kOe leads to fragmentation of ferromagnetic clusters and then to an increase in the degree of polarization of local spins of manganese and the emergence of long-range ferromagnetic order. With increasing magnetic field up to 140 kOe, the magnetic ordering temperature reaches 160 K. The causes of the structural and magnetic phase separation of this composition and formation mechanism of its spin-glass magnetic state are analyzed.     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

Magnetic excitations in antiferromagnetic Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>

Magnetic excitations in the antiferromagnetic Bi₂CuO₄ (T _N =42K) are investigated on the basis of anisotropic exchange interaction between spins of Cu²⁺ ions. We calculate the dispersion curves and evaluate the intensity of the inelastic neutron scattering by spin wave excitations. Spin contraction at OK and the effect of spin wave interaction are studied.     

Peculiarities of magnetic phase separation in anion-deficient La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>MnO<Subscript>2.85</Subscript> manganite

The temperature and field dependences of the specific magnetic moment of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite have been measured. It is established, that the magnetic state of the sample studied is a cluster spin glass and it is the result of frustration of exchange Mn³⁺-O-Mn³⁺ interactions due to the redistribution of oxygen vacancies. The increase of the magnetic field leads to an increase in the degree of polarization of local spins of manganese. It is established using the magnetic criterion that a phase transition into the paramagnetic state for the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite is a thermodynamic second order phase transition. The causes and mechanism of the magnetic phase separation are discussed.     

Frustrated exchange interactions formation at low temperatures and high hydrostatic pressures in La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>Mn<Subscript>O2.85</Subscript>

The magnetic and thermal properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite are investigated in wide temperature (4–350 K) range, including under hydrostatic pressure (0–1.1 GPa). Throughout the pressure range investigated, the sample is spin glass with diffused phase transition into paramagnetic state. It is established, that spin glass state is a consequence of exchange interaction frustration of the ferromagnetic clusters embeded into antiferromagnetic clusters. The magnetic moment freezing temperature T _f of ferromagnetic clusters increases under pressure, freezing temperature dependence on pressure is characterized by derivative value ∼4.5 K/GPa, while the magnetic ordering T _MO temperature dependence is characterized by derivative value ∼13 K/GPa. The volume fraction of sample having ferromagnetic state is V _fer ∼ 13% and it increases under a pressure of 1.1 GPa by ΔV _fer ≈ 6%. Intensification of ferromagnetic properties of the anion-deficient La_0.70Sr_0.30MnO_2.85 manganite under hydrostatic pressure is a consequence of oxygen vacancies redistribution and unit cell parameters decrease. The most likely mechanism of frustrated exchange interactions formation is discussed.     

Magnetic and ferroelectric ordering in BiMn<Subscript>2</Subscript>O<Subscript>5</Subscript> oxide

A group-theoretical analysis of the magnetic phase of BiMn₂O₅ oxide is performed using the space symmetry group of the compound. Using the projection operator method, we determine the basis functions of the irreducible representation of the space group, which are expressed in terms of the magnetic vector components. This representation can govern two phase transitions from the paramagnetic state to the antiferromagnetic phase with close temperatures and ordering of the spins of manganese ions in two crystallographic positions. It is found from renorm group analysis of these transitions that when these transitions occur as second- order transitions, the electric polarization does not appear in the system because spin fluctuations in this case elevate the symmetry of the system. Polarization appears when at least one of these transitions becomes a first-order transition as a result of spin fluctuations.     

Effect of Gd-Mn exchange on phase transitions in GdMn<Subscript>2</Subscript>O<Subscript>5</Subscript> induced by a strong magnetic field

Complex studies of the magnetic, magnetoelectric, and magnetoelastic properties of GdMn₂O₅ single crystals in strong pulsed magnetic fields are carried out in order to obtain additional indirect information on the character of the rare-earth and manganese spin ordering. It is shown that magnetic ordering of Gd³⁺ spins affects the manganese sublattice spin orientation and initiates new magnetic phase transitions. The observed magnetoelectric properties of the GdMn₂O₅ system are interpreted in terms of the theory of phase transitions.     

Valence and magnetic states of impurity iron ions in the La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Co<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> perovskite

The local magnetic and valence states of impurity iron ions in the rhombohedral La_0.75Sr_0.25Co_0.98 ⁵⁷Fe_0.02O₃ perovskite were studied using Mössbauer spectroscopy in the temperature range 87–293 K. The Mössbauer spectra are described by a single doublet at 215–293 K. The spectra contained a paramagnetic and a ferromagnetic component at 180–212 K and only a broad ferromagnetic sextet at T < 180 K. The results of the studies showed that, over the temperature range 87–295 K, the iron ions are in a single (tetrahedral) state with a valence of +3. In the temperature range 180–212 K, two magnetic states of Fe³⁺ ions were observed, one of which is in magnetically ordered microregions and the other, in paramagnetic microregions; these states are due to atomic heterogeneity. In the magnetically ordered microregions in the temperature range 87–212 K, the magnetic state of the iron ions is described well by a single state with an average spin S = 1.4 ± 0.2 and a magnetic moment μ(Fe) = 2.6 ± 0.4μ _B .     

Electronic structure of half-metallic ferromagnet Co<Subscript>2</Subscript>MnSi at high-pressure

In this study, first principles calculation results of the half-metallic ferromagnetic Heusler compound Co₂MnSi are presented. All calculations are based on the spin-polarized generalized gradient approximation (σ-GGA) of the density functional theory and ultrasoft pseudopotentials with plane wave basis. Electronic structure of related compound in cubic L2₁ structure is investigated up to 95 GPa uniform hydrostatic pressure. The half-metal to metal transition was observed around ~70 GPa together with downward shift of the conduction band minimum (CBM) and a linear increase of direct band gap of minority spins at Γ-point with increasing pressure. The electronic density of states of minority spins at Fermi level, which are mainly due to the cobalt atoms, become remarkable with increasing pressure resulting a sharp decrease in spin polarization ratio. It can be stated that the pressure affects minority spin states rather than that of majority spins and lead to a slight reconstruction of minority spin states which lie below the Fermi level. In particular, energy band gap of minority spin states in equilibrium structure is obviously not destroyed, but the Fermi level is shifted outside the gap.     

Magnetic behaviour of nano-particles of Fe<Subscript>2.9</Subscript>Zn<Subscript>0.1</Subscript>O<Subscript>4</Subscript>

DC magnetization measurements are reported in the temperature range 20–100 K on a poly-disperse nano-particle sample of the spinel ferrite Fe_2.9Zn_0.1O₄ with a log-normal size distribution of median diameter 43.6 Å and standard deviation 0.58. Outside a core of ordered spins, moments in surface layer are disordered. Results also show some similarities with conventional spin glasses. Blocking temperature exhibits a near linear variation with two-third power of the applied magnetic field and magnetizationM evolves nearly linearly with logarithm of timet. Magnetic anisotropy has been estimated by analysing theM-logt curve. Anisotropy values show a large increase over that of bulk particle samples. Major contribution to this enhancement comes from the disordered surface spins.     

Magnetic susceptibility in quasi one-dimensional Ba<Subscript>a2</Subscript>V<Subscript>3</Subscript>O<Subscript>9</Subscript>: chain segmentation versus the staggered field effect

A pronounced Curie-like upturn of the magnetic susceptibility χ( T ) of the quasi one-dimensional spin chain compound Ba₂V₃O₉ has been found recently [#!kaul:02!#]. Frequently this is taken as a signature for a staggered field mechanism due to the presence of g-factor anisotropy and Dzyaloshinskii-Moriya interaction. We calculate this contribution within a realistic structure of vanadium 3 d- and oxygen 2 p-orbitals and conclude that this mechanism is far too small to explain experimental results. We propose that the Curie term is rather due to a segmentation of spin chains caused by broken magnetic bonds which leads to uncompensated S = ? spins of segments with odd numbers of spins. Using the finite-temperature Lanczos method we calculate their effective moment and show that ∼ 1% of broken magnetic bonds is sufficient to reproduce the anomalous low-T behavior of χ( T ) in Ba₂V₃O₉. Received 19 December 2002 / Received in final form 29 January 2003 Published online 14 March 2003     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Models of spin structures in Sr<Subscript>2</Subscript>RuO<Subscript>4</Subscript>

The mean-field method is used to calculate the bands, Fermi surfaces, and spin susceptibilities of a three-band model of the RuO₄ plane of Sr₂RuO₄ rutinate for states with different spin structures. In particular, the spiral state is studied with the “incommensurate” vector Q=2π(1/3, 1/3) corresponding to the nesting of bands with the population n=4. This state proves to be the lowest with respect to energy among other (paramagnetic, ferromagnetic, antiferromagnetic, and periodic) solutions. In the spiral state, in addition to the main α, β, and γ sheets of the Fermi surface, shadow Fermi boundaries along the Γ(0, 0)-M(π, 0) line (previously observed in the ARPES experiments) are revealed and explained. This may change the interpretation of the data on dispersionless peaks in photoemission, previously ascribed to surface states. The spin susceptibilities of the spiral state exhibit peaks in the dependence Im?(q, ω) at q=Q in accordance with the observed magnetic peak in neutron scattering. The hypothesis of the presence of spin structures with q=Q in the normal state of Sr₂RuO₄ and the methods of checking this hypothesis are discussed.     

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.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

On the magnetism of Ln<Subscript>2/3</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> (Ln = lanthanide)

The magnetic and thermodynamic properties of the complete Ln_2/3Cu₃Ti₄O₁₂ series were investigated. Here Ln stands for the lanthanides La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. All the samples investigated crystallize in the space group Im[`3]Im\bar{3} with lattice constants that follow the lanthanide contraction. The lattice constant of the Ce compound reveals the presence of Ce⁴⁺ leading to the composition Ce_1/2Cu₃Ti₄O₁₂. From magnetic susceptibility and electron-spin resonance experiments it can be concluded that the copper ions always carry a spin S = 1/2 and order antiferromagnetically close to 25 K. The Curie-Weiss temperatures can approximately be calculated assuming a two-sublattice model corresponding to the copper and lanthanide ions, respectively. It seems that the magnetic moments of the heavy rare earths are weakly coupled to the copper spins, while for the light lanthanides no such coupling was found. The 4f moments remain paramagnetic down to the lowest temperatures, with the exception of the Tm compound, which indicates enhanced Van-Vleck magnetism due to a non-magnetic singlet ground state of the crystal-field split 4f manifold. From specific-heat measurements we accurately determined the antiferromagnetic ordering temperature and obtained information on the crystal-field states of the rare-earth ions.     

Magnetic and electrical properties of the ZnGeAs<Subscript>2</Subscript>: Mn chalcopyrite

Doping of the ZnGeAs₂ semiconductor with manganese has produced compositions with spontaneous magnetization and high Curie temperatures of up to 367 K for the composition 3.5 wt% Mn. Their magnetic properties are characteristic of spin glasses at temperatures T < T _S and magnetic fields H < 11 kOe. In stronger fields, the spin glass state transforms into a phase with a spontaneous magnetization 4–5 times weaker than that to be expected under ferromagnetic ordering of all Mn ions. This is obviously a singly-connected ferromagnetic phase containing regions with frustrated bonds. The frustrated regions and the spin glass phase have inclusions of noninteracting ferromagnetic clusters, because these regions and the spin glass phase at low temperatures exhibit a strong increase in the magnetization M, with the dependence M(T) being described by the Langevin function. Measurements of the electrical resistivity ρ and the Hall effect have revealed that, for T < 30 K, the resistivity ρ of compositions with 1.5 and 3.5 wt % Mn is higher that at 30 K, which makes superexchange dominant and gives rise to the onset of the spin glass state. The nonuniform distribution of Mn ions in the spin glass phase accounts for the existence of isolated ferromagnetic clusters, their ferromagnetism being generated by carrier-mediated exchange. As the temperature increases still more, the increase in the mobility occurs faster than the decrease in the concentration, thus promoting an enhancement of the carrier-mediated exchange and growth of the ferromagnetic clusters in size, which at T = T _S come in contact. This signifies a transition from a multiply-to a singly-connected ferromagnetic phase, which contains microregions with frustrated bonds.     

O<Subscript>2</Subscript> photodesorption from a Ag<Subscript>8</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> cluster

The decay path of an Ag₈(O₂)^- cluster photoexcited by a 3.1 eV photon is elucidated using time-resolved photoelectron spectroscopy. Photoabsorption results in the formation of an excited state giving rise to a peak in the photoelectron spectra with well-resolved vibrational finestructure. With a lifetime of about 100 fs this bound state decays into an anti-bonding state which dissociates into O₂ and Ag₈^- on a timescale of 10 ps. In the photoelectron spectra, this corresponds to a broad maximum shifting gradually towards higher binding energy while the O₂ and Ag₈^- separate. Finally, the spectrum of bare Ag₈^- appears. This process is unique to small clusters, because on metal surfaces excited state lifetimes are too short to allow for direct dissociation.