Hydrogen bonds mediated magnetism in Cu(bmen)2Pd(CN)4

Results of synthesis, X-ray structure analysis, electron spin resonance, susceptibility, magnetization and specific heat measurements of powdered Cu(bmen)₂Pd(CN)₄ (,N^′-dimethyl-1,2-diaminoethane) are reported. Its structure is formed of quasi-linear chains of the [-Cu(bmen)₂-NC-Ni(CN)₂-CN-]_n composition; these are interlinked by hydrogen bonds (HBs) leading to two-dimensional patterns. Upon magnetic, spectral and thermodynamic measurements the compound was identified as an S=1/2 Heisenberg antiferromagnet on a square lattice with due to the dominant role of HBs in creating a square network. The long-range ordering observed at 0.24 K is proposed to be of a Néel type. The possibility of tuning the exchange interactions in various directions is considered.     

Magneto-optical measurement on the layer type magnet (CH2)2(ND3)2MnCl4

The linear birefringence (LB) of the antiferromagnet (CH₂)₂(ND₃)₂MnCl₄ has been measured as a function of temperature and in magnetic fields up to 100 kOe. The temperature dependence of the LB points to a pronounced two dimensional magnetic behaviour. No anomaly corresponding to the effect of three dimensional ordering could be detected at T_N. In theffield dependent measurements the spin flop at H_SF = 33.6 ± 1 kOe (T = 4K) could clearly be detected.     

Core electron ionization energies and electronic structure of Ti(NO3)4 and Cu(NO3)2

Gas phase X-ray photoelectron spectra of Ti(NO₃)₄ and Cu(NO₃)₂ are reported and discussed in terms of the molecular charge distributions. No measurable splitting is observed between the 1s ionization energies of the chemically distinct oxygen atoms in either molecule. Ab initio calculations for Cu(NO₃)₂ suggest that this is due in large measure to differential orbital relaxation occurring upon core electron ionization.     

Raman intensity measurements of the Fermi diad ν1, 2ν2 in CO2 and CO2

Intensity measurements of the ν₁, 2ν₂ vibrational Raman bands of ¹²CO₂ and ¹³CO₂ lend support to Amat's suggestion that the unperturbed 02⁰0 level is above the 10⁰0 level for ¹²CO₂. For ¹³CO₂, however, the ordering of the levels is reversed.     

Proton magnetic resonance study of the phase transitions of [N(CH3)4]2BCl4 (B=Co, Cu, Zn, and Cd) single crystals

The proton spin-lattice relaxation rates in [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals grown using the slow evaporation method were investigated over the temperature range 120-400 K. It was found that the relaxation processes of ¹H for all the [N(CH₃)₄]₂BCl₄ crystals can be described with single exponential functions. The changes in the ¹H relaxation behavior in the neighborhood of the phase transition temperatures are used to detect changes in the state of internal motion. From the ¹H spin-lattice relaxation rate measurements for [N(CH₃)₄]₂BCl₄ crystals, the activation energies were calculated for each phase. The large values of the activation energies indicate that the N(CH₃)₄ groups are significantly affected during the transitions. Although these [N(CH₃)₄]₂BCl₄ crystals all belong to the group of A₂BX₄-type crystals, their ¹H spin-lattice relaxation rates have different temperature dependences and indicate the occurrence of different molecular motions within the crystals. We additionally show for the first time that the differences in ¹H spin-lattice relaxation rates among the [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals arise from differences in the electron structures of the metal ions within the series.     

X-ray diffraction and spectroscopic investigations of phase transitions in linear chain compounds M2 [Pt(CN)4]3 · 21H2O,with M = Dy, Er,Tb, Y

Phase transitions of single-crystal M₂ [Pt(CN)₄]₃ · 21H₂O are investigated under temperature variation using X-ray diffraction, polarized emission and DSC-measurements. At a temperature T_trans a jump was observed in lattice parameters and in optical transition energies. The transition is connected with an occurence of a latent transition enthalpy. This indicates a displacive phase transition of first order. Optical and X-ray data can be correlated.     

Amorphous Ni-Al underlayer-accelerated L10 ordering transition of FePt thin films

In the present study, we succeeded in accelerating the L1₀ ordering transition of FePt thin films by employing amorphous Ni-Al as underlayers. The coercivity H_c = 5 kOe and ordering parameter S = 0.67 of FePt thin films deposited on a Ni-Al underlayer with a thickness of ∼5 nm after 380 °C annealing for 30 min are significantly higher than those H_c = 0.4 kOe and S = 0.35 of the films without the Ni-Al underlayer. The L1₀ ordering process of and the coercivity of FePt thin films can be significantly tuned by varying the thickness of the Ni-Al underlayer.     

EPR studies of linewidth anomalies at phase transitions in [N(C2H5)4]2MnCl4

We have studied [N(C₂H₅)₄]₂MnCl₄ crystal by X-band CW EPR spectra in the temperature range 170-300 K. The angular dependences of linewidth ΔH were measured and described in the light of a double-layer system (2D) with exchange interactions. Two temperature anomalies of linewidth ΔH were found at T₁=225 K and T₂=192 K on cooling. Different behaviors of ΔH anomalies recorded for an external magnetic field parallel and perpendicular to the ab crystallographic plane indicate ordering/disordering of MnCl₄ groups in this plane and their displacement along the c-axis which occurs in the temperature of about 225 K.     

Selected properties of EuCo2(Si1−xGex)2 alloys

EuCo₂(Si_1−xGe_x)₂, x=0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 samples were synthesised by induction melting followed by annealing at 900 °C and rapid quenching. X-ray powder diffraction and Auger electron spectroscopy studies revealed that solid solutions are formed only for x?0.2 and x?0.7. Magnetic susceptibility investigations for the solid solutions revealed a dominant divalent europium valence state in the germanium-rich samples and a dominant trivalent europium component in the silicon-rich samples. In the germanium-rich samples, a long-range antiferromagnetic ordering was observed. In all samples studied, additional magnetic transitions at various temperatures were detected, which could be attributed to small clusters containing different europium chemical surrounding from that in the predominant phase.     

L10 FePt thin films with [0 0 1] crystalline growth fabricated by SiO2 addition—rapid thermal annealing and dot patterning of the films

FePt films that have a high degree of order S in their L1₀ structure (S>0.90) and well-defined [0 0 1] crystalline growth perpendicular to the film plane were fabricated on thermally oxidized Si substrates by the addition of an oxide and successive rapid thermal annealing (RTA). The mechanism of L1₀ ordering and [0 0 1] crystalline growth perpendicular to the film plane arising through the oxide addition and RTA process is also discussed. The L1₀ ordering (S>0.90) and the [0 0 1] crystalline growth were achieved by (1) lowering the activation energy due to in-plane tensile stress and the initiation of L1₀ ordering at a low temperature, (2) [0 0 1] crystalline growth through in-plane tensile stress, and (3) enhancement of atomic diffusion via the addition of an oxide and the resultant lowering of the ordering temperature. Effect (1) was observed in the case of SiO₂ addition, effect (2) was generally observed in the case of oxide addition and the RTA process, and effect (3) was prominent in the case of ZnO addition. With the addition of ZnO, the L1₀ ordering started at below 400 °C and was completed at 500 °C. Finally, dot patterns were successfully fabricated down to a diameter of 15 nm using electron beam lithography, and the magnetic state of the dot pattern was observed by magnetic force microscopy.     

Origin of the satellite Kβ10 in X-ray spectra

The transition energies corresponding to the transition array KM_x→M_xM_2,3 (x = 1, 2, 3, 4, 5) have been calculated using Slater formulas for interaction between two holes in inner shells and HFS values of electrostatic Slater integrals. The initial and final state energies have been corrected for the adiabatic relaxation of atomic orbits, which take place due to creation of an inner vacancy. The value of this adiabatic relaxation energy for KM states has been calculated semi-empirically by comparing the KM₁³S₁→L₃M₁³P₂ transition energies with the measured Kα₁ line energies. For the final state, this value has been taken from available literature[21]. It is found that the satellite β₁₀ in the K-emission spectra of Zn, Ga, Ge, Mo and Rh is emitted by the superposition of more than one transition of the array. Consideration of the relative transition probabilities shows that the major contribution to β₁₀ comes from a K→M_2,3 transition in the presence of a 3d spectator vacancy. It has been suggested that the satellite β′₁ (7655.5 eV, Edamoto 1950) in the K-emission spectrum of cobalt, and the satellite β₇ (8271.2 eV) in the K-spectrum of nickel should be reidentified as β₁₀. It has been shown that the two lines β′₁ (8268.0 eV) and β″₁(8270.3 eV) observed[13] in the nickel Kβ spectrum are two components of the satellite β₁₀, and it is hence suggested that these should be renamed β₁₀⁽¹⁾ and β₁₀⁽²⁾ respectively. Similarly, the lines β″₍₁₎ (8909.3 eV) and β″₍₂₎(8913.0 eV) in the CuKβ spectrum are proved to be two components of β₁₀ and hence should be renamed β₁₀⁽¹⁾ and β₁₀⁽²⁾ respectively.     

Optical constants of Cu(In0.7Ga0.3)5Se8 and Cu(In0.4Ga0.6)5Se8 crystals

Variable angle spectroscopic ellipsometry has been applied to characterize the optical constants of bulk Cu(In_0.7Ga_0.3)₅Se₈ and Cu(In_0.4Ga_0.6)₅Se₈ crystals grown by the Bridgman method. The spectra were measured at room temperature over the energy range 0.8-4.4 eV. Adachi’s model was used to calculate the dielectric functions as well as the spectral dependence of complex refractive index, absorption coefficient, and normal-incidence reflectivity. The calculated data are in good agreement with the experimental ones over the entire range of photon energies. The parameters such as strength, threshold energy, and broadening, corresponding to the E₀, E_1A, and E_1B interband transitions, have been determined using the simulated annealing algorithm.     

A line parameter list for the ν2 and ν4 bands of 12CH4 and 13CH4, extended to J′ = 25 and its application to planetary atmospheres

Line parameters (transition frequencies, line strengths, line widths, ground state energies and quantum identifications) for the ν₂ and ν₄ bands of ¹²CH₄ and ¹³CH₄ have been calculated for J'?25 using the simultaneous coupled fitting procedure of Gray and Robiette. Molecular constants for the ν₂ band of ¹³CH₄ were estimated from isotopic shifts from ¹²CH₄ values. Agreement with laboratory spectra, where available, is always well within 1 cm^-1 over the entire spectral range covered by the list. The most serious problem in comparison with laboratory data is the omission of lines belonging to “hot” bands in this spectral region. This list is valuable in remote sensing problems for sorting out lines of trace species from weak methane lines and for determining the atmospheric opacity in relatively transparent spectral regions. Applications of the parameter list are demonstrated for remote sounding of the Jovian atmosphere. The list is available on magnetic tape from the authors.     

FePt L10 ordering and grain growth using millisecond pulse laser processing

The structural and magnetic properties of ∼12 nm thick FePt thin films grown on Si substrates annealed using a 1064 nm wavelength laser with a 10 ms pulse have been examined. The A1 to L1₀ ordering phase transformation was confirmed by electron and X-ray diffraction. An order parameter near 50% and a maximum coercivity of 12 kOe were obtained with laser energy densities of 25-32 J/cm². Grain growth, quantified by dark field transmission electron microscopy, occurred during chemical ordering at the laser pulse widths studied.     

Immiscibility in the Fe3O4-FeCr2O4 spinel binary

A recent thermodynamic model of mixing in spinel binaries, based on changes in cation disordering (x) between tetrahedral and octahedral sites [Am. Mineral. 68 (1983) 18, 69 (1984) 733], is investigated for applicability to the Fe₃O₄-FeCr₂O₄ system under conditions where incomplete mixing occurs. Poor agreement with measured consolute solution temperature and solvus [N. Jb. Miner. Abh. 111 (1969) 184] is attributed to neglect of: (1) ordering of magnetic moments of cations in the tetrahedral sublattice antiparallel to the moments of those in the octahedral sublattice and (2) pair-wise electron hopping between octahedral site Fe³⁺ and Fe²⁺ ions. Disordering free energies (ΔG_D), from which free energies of mixing are calculated, are modeled by

     

Cavity size versus anion size in (TMTSF)2X salts: Possible implications for the uniqueness of (TMTSF)2C104

A simple, effective method for deducing the fit of the complex anion, X, within its structural cavity for (TMTSF)₂X salts with tetrahedral anions is presented. Subsequent analysis suggests that an electronic instability is operative over the full range of salts, becoming coincident with or leading to anion ordering and an insulating ground state above some critical fit of the anion within its structural cavity. Moreover, (TMTSF)₂C10₄ can be considered unique in that the perchlorate anion is too small for anion ordering to be the critical instability, yet large enough for anion ordering to occur at a finite temperature.     

Impurity-induced magnetic order in the mixture of two spin gap systems (CH3)2CHNH3CuCl3 and (CH3)2CHNH3CuBr3

The ground state of the solid solution of the two spin gap systems (CH₃)₂CHNH₃CuCl₃ and (CH₃)₂CHNH₃CuBr₃ has been investigated by ¹H NMR. The existence of a magnetic ordering in the sample with the Cl-content x=0.85 was clearly demonstrated by a drastic splitting in a resonance line at low temperatures below T_N=13.5 K. The observed NMR spectra in the ordered state was qualitatively consistent with the simple antiferromagnetic state.     

UV and X-ray-excited photoelectron spectra of trifluoromethylgermanes (CF3)4−nGeHn(n = 1–3)

He(I), He(II) and X-ray-excited photoelectron spectra of the trifluoromethylgermanes (CF₃)_4?nGeH_n(n = 1–3) are reported. Assignments of the valence region are made on the basis of semi-empirical CNDO/2 calculations, comparisons with the spectra of related series of molecules, band shapes, and relative-intensity changes between features in the He(I) and He(II) spectra. Core-level binding energies are also compared with those of related species, and the usefulness of CNDO/2 and EESOP charge calculations is examined.     

Preferential ordering of Mn and Fe Atoms in Y6(Fe1−xMnx)23

Neutron diffraction studies of the nomagnetic compositional range of the Y₆(Fe_1?xMn_x)₂₃ system reveal the presence of preferential ordering of Fe and Mn atoms on the four transition metal crystallographic sites. Throughout the entire compositional range of the ternary system, Mn atoms prefer to occupy the f₂ site and Fe atoms the f₁ site. Refinements of the data were carried out using the Rietveld profile method.