Magnetic interactions in the layer compounds MPX3 (M = Mn,Fe, Ni; X = S,Se)

The mpx₃ phases (M = Mn, Fe, Ni; X = S, Se) with sheet structures are insulators with localized moments. They show antiferromagnetic ordering at low temperatures. From the magnetic structures determined by neutron diffraction the magnetic interactions are considered and shown to be characteristic of 2D behavior.     

Further neighbour interactions in the quasi b.c.c. Heisenberg ferromagnets M2 Cu X4 · 2H2 O (M = NH4, K,Rb or Cs; X = Cl or Br)

The Curie-Weiss constant θ of the quasi b.c.c., $\text{S =}\text{1}\text{2}$, Heisenberg ferromagnets, (NH₄)₂ Cu Br₄ · 2H₂ O and Rb₂ Cu Br₄ · 2H₂ O, have been derived from measurements of the susceptibility in the paramagnetic region (4.2 < T < 100 K) and of the high-field magnetization curves at $\text{T = 4.2}\text{K}\text{(}\text{T}\text{T}{}_{\mathrm{c}}\text{? 2.3)}$. The $\text{T}{}_{\mathrm{c}}\text{θ}$ values obtained point to the presence of further neighbour interactions considerably stronger than previously assumed. The effective number of equivalently interacting magnetic neighbours is estimated to be at least seventeen.     

Magnetic properties of the compounds N(CH3)4MnIIMIII(CN)6 ·8 H2O(MIII = Mn,Fe)

In the isostructural cyanobridged chain compounds N(CH₃)₄Mn^IIM^III(CN)₆ · 8H₂O high spin Mn(II) ions couple antiferromagnetically to low spin Mn(III) of Fe(III) ions. The Mn^II–Mn^III compound orders ferrimagnetically below T_N = 28.5 ± 1 K. The tetragonal a and b axes are easy ones for the magnetic moments. In the Mn^II–Fe^III compound antiferromagnetic order occurs below T_N = 9.3 K, with spins aligned along the tetragonal c axis. The compound undergoes a meta-magnetic transition from the antiferromagnetic to a ferrimagnetic phase. This occurs at 2 K for a field H_crit ≈ 1.2 T. The temperature dependence of H_crit, which vanishes at T_N, is followed. The tricritical temperature T¹ is ～ 5 K.     

The rotational spectrum of BiO radical in its X1Π1/2 and X2Π3/2 states

Rotational spectra have been observed for BiO produced in a DC discharge through a low pressure mixture of O₂, Ar, and Bi vapor. Because of the highly non-thermal distribution of states, it has been possible to observe spectra arising from the X₁²Π_1/2 level up to v = 9 and for the X₂²Π_3/2 level up to v = 5 near 10 538 cm⁻¹. Precise rotational and hyperfine parameters have been determined for the observed states. By using available near infrared (NIR) data in a merged fit, the 0-0 and 1-1 fine structure intervals have been more precisely determined. Although the quality of the fit is very good, the interpretation of the hyperfine constants is complicated by relativistic effects and the interaction of the X₂ state with A₁⁴Π_3/2 state. The magnetic and quadrupole coupling constants will be compared with those of the Bi atom and related molecules.     

Chemical shifts of copper and cobalt K absorption discontinuities in the spinels CuCr2X4 (X =O,S, Se,Te), CoCr2X4 (X =O,S) and Cu0.5Co0.5Cr2−xRhxS4 (x = 0, 1, 2)

The present paper reports the chemical shifts of the copper and cobalt K absorption discontinuities in the spinels CuCr₂X₄ (X = O, S, Se, Te), CoCr₂X₄ (X = O, S) and Cu_0.5Co_0.5Cr_2?xRh_xS₄ (x = 0, 1, 2). The magnitudes of the chemical shifts show that copper is monovalent (except in CuCr₂O₄) and cobalt is bivalent in all these spinels. The valence structure for the spinels containing copper shows that the conductivity of such spinels (except CuCr₂O₄) is due to the holes in the anion p-orbitals. Levine's theory of ionicity has been extended to spinels which has made it possible to calculate the various bond parameters for the spinels CuCr₂X₄ and CoCr₂X₄. It has been found that a linear relation exists between the X-ray chemical shift ΔE and C, E_g, and f_i, the ionic energy, total energy and ionici parameters respectively. This fact has been used to determine the various bond parameters in the spinels Cu_0.5Co_0.5Cr_2?xRh_xS₄. It is found that in these spinels a natural balance of ionicity at the A site is maintained, when chromium is gradually replaced by rhodium.     

Tunable dielectric response of transition metals dichalcogenides MX2 (M=Mo,W; X=S,Se, Te): Effect of quantum confinement

The first principle calculations have been performed to study the influence of number of layers on the dielectric properties of dichalcogenides of Mo and W for in-plan (E⊥c)$(E\perp c)$ as well as out-of-plan polarization (E∥c)$(E\parallel c)$. We have taken bulk, mono, bi, four and 6-layer setup for this study. The EELS shows significant red shift in the energies of π$\pi$ plasmons, while prominent red shift has been found for the energies of (π+σ)$(\pi +\sigma )$ plasmons of all the studied materials by reducing the number of layers from bulk to monolayer limit. The ?_s${?}_s$ has been found to red shifted by 62.5% (66.3%), 48.5% (62.1%), 52.7% (66.2%), 61.7% (64.6%), 61.5% (66.7%) and 62.5% (70.5%) from bulk values of MoS₂, MoSe₂, MoTe₂, WS₂, WSe₂, WTe₂ respectively for E⊥c$E\perp c$(E∥c)$(E\parallel c)$ as one goes from bulk to monolayer of these materials. The interband transitions are found to remain independent of the number of layers, however their intensity decreases with decrease in the number of layers. The dielectric functions are highly anisotropic in low energy range and becomes isotropic in high energy range.     

Correlation between energy levels of linear and bent X2Y2 molecules

The permutation-inversion group developed by Longuet-Higgins is extended to a classification of the vibronic, torsional, and rotational wavefunctions of a nonrigid X₂Y₂ molecule by introducing a symmetry operation $\text{T}\text{?}$, which rotates the top half of the molecule by 2π and, accordingly, the molecule-fixed x axis by π. Since the energy levels of linear (D_∞h) and bent (C_2h, C_2h, and C₂) forms of X₂Y₂ are classified according to a set of common symmetry operations of this extended permutation-inversion group, their energy levels can be correlated, including those of nonrigid forms such as a quasilinear system or a free internal rotor. Nuclear spin weights and selection rules are derived.     

ESR and photoacoustic spectra of V2O5−MO2 (M = Se, Te, Ge) glasses

ESR spectra of V₂O₅?MO₂ (M = Ge, Se, Te) glasses are investigated in the range 298–498 K. The spectra at 298 K are characteristic of V⁴⁺ with the 3d¹ electron localized on a single ${}^{51}\text{V}\text{(I =}\text{7}\text{2}$) in the glass network. At higher temperature, the hyperfine structure progressively broadens, leading eventually to a broad, single ESR peak. These results are consistent with thermally-induced electron hopping from V⁴⁺ to V⁵⁺. Photoacoustic spectra of the glass at 298 K are characteristic of V⁴⁺ in a distorted octa environment. A correlation of ESR and PAS data suggests that covalency increased as M is charged from Ge through Te to Se.     

Preparation and characterization of Cu(In,Ga)(Se,S)2 films without selenization by co-sputtering from Cu(In,Ga)Se2 quaternary and In2S3 targets

In this study, Cu(In,Ga)(Se,S)₂ (CIGSS) thin films were deposited onto a bi-layer Mo coated soda-lime glass by co-sputtering a chalcopyrite Cu(In,Ga)Se₂ (CIGS) quaternary alloy target and an In₂S₃ binary target. A one-stage annealing process was performed to form CIGSS chalcopyrite phase without post-selenization. Experimental results show that CIGSS films were prepared by the proposed co-sputter process via CIGS (70 W by radio frequency) and In₂S₃ (30 W by direct current) with a substrate temperature of 373 K, working pressure of 0.67 Pa, and one-stage annealing at 798 K for 30 min. The stoichiometry ratios of the CIGSS film were Cu/(In + Ga) = 0.92, Ga/(In + Ga) = 0.26, and Se/(S) = 0.49 that approached device-quality stoichiometry ratio (Cu/(In + Ga) < 0.95, Ga/(In + Ga) < 0.3, and (Se/S) ≈ 0.5). The resistivity of the sample was 14.8 Ω cm, with a carrier concentration of 3.4 × 10¹⁷ cm⁻³ and mobility of 1.2 cm² V⁻¹ s⁻¹. The resulting film exhibited p-type conductivity with a double graded band-gap structure.     

The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands of 15NH3

The ir absorption of gaseous ¹⁵NH₃ between 510 and 3040 cm^?1 was recorded with a resolution of 0.06 cm^?1. The ν₂, 2ν₂, 3ν₂, ν₄, and ν₂ + ν₄ bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. ?pirko, J. M. R. Stone, and D. Papou?ek (J. Mol. Spectrosc.60, 159–178 (1976)). A set of effective molecular parameters for the ν₂ = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν₄ and ν₂ + ν₄ bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν₄ in ¹⁴NH₃ by ?. Urban et al. (J. Mol. Spectrosc.79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.     

Large single-ion anisotropy and ferromagnetic intrachain interaction in four Ni-compounds of formula NiX2L2 with X = Cl,Br; L = N2C3H4, NC5H5

The specific heat has been measured of powdered samples of NiX₂L₂ (X = Cl, Br; L = pyrazole, pyridine), compounds which can be considered as weakly antiferromagnetically coupled ferromagnetic chains with large uniaxial single-ion anisotropy. The intrachain exchange constants and the zero-field splitting parameters for the four compounds have been deduced from the specific heat data, using accurate numerical calculations for the isotropic Heisenberg spin S = 1 linear chain model with uniaxial single-ion anisotropy.     

LiBX2 (B=Ga, In; X= S, Se, Te)光学性质与力学性质的第一性原理计算

采用基于第一性原理的赝势平面波方法系统地计算了LiBX₂ (B= Ga, In; X= S,Se,Te) 晶体的光学性质与力学性质. 由禁带宽度推断出晶体抗激光损伤阈值的大小顺序为LiGaS₂ > LiInS₂ > LiGaSe₂ > LiInSe₂ > LiGaTe₂ > LiInTe₂. 六种晶体在常压下均满足机械力学稳定性要求, 且铟化合物可塑性及延展性强于镓化合物. 这些晶体的静态电介电常数 ε₁(0)、静态折射率n(0)和双折射率Δn 理论计算值与实验值相符. LiGaS₂, LiInS₂, LiGaSe₂, LiInSe₂和LiGaTe₂五种化合物双折射率较高, 并且它们的吸收谱与反射谱在中远红外区是透过的, 因此可推断出这五种化合物可以成为优异的中远红外非线性光学材料.     

A theoretical model for the interacting upper states of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands in methane

The effective vibration-rotation Hamiltonians complete to fourth order in the Amat-Nielsen scheme for the upper states of the ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ bands in methane are reviewed, and the major vibration-rotation interactions (H₃₀, $\text{H}\text{?}{}_{40}$, $\text{H}\text{?}{}_{21}$, $\text{H}{}_{31}$, $\text{H}\text{?}{}_{22}$) connecting the different vibrational states are discussed. Explicit matrix elements in a basis of harmonic oscillator-symmetric rotor basis functions are given for the purely vibrational terms and for the vibration-rotation interactions. Expressions for spectral intensities of infrared and Raman spectra are presented, and the selection rules and transition moment matrix elements are stated. A computer program is described which, incorporating all these features, can be used for prediction of infrared and Raman spectra and for determination of molecular constants from observed spectra by a least-squares routine. As an example the program is applied to the 2ν₄ isotropic Raman spectrum of ¹²CH₄, leading to a very good agreement between the experimental and calculated spectra.     

Investigation of the solid solution series 2(MnX)-CuInX2 (X=S, Se)

(2MnX)_x(CuInX₂)_1−x with X=S and Se were prepared by solid state reaction from the end members α-MnS, β-MnS and CuInS₂ in the range 0<x≤0.2 (≤0.6 for β-MnS) as well as MnSe and CuInSe₂ in the range 0<x≤0.1. Mixed crystals with 0≤x≤0.1 crystallize in the tetragonal chalcopyrite type structure, (2α-MnS)_x(CuInS₂)_1−x samples with 0.1<x≤0.2 and (2β-MnS)_x(CuInS₂)_1−x samples up to x=0.6 consist of two phases, occuring as tetragonal domains (x∼0.1 for X=S) within a cubic matrix with zinc-blende type structure (x∼0.4 for X=S), indicating a miscibility gap. For tetragonal single phase samples the band gap energy, the lattice constants and the anion parameter have been determined. The first and the latter ones show a different composition dependent behaviour caused by the modification of the MnS (α-MnS with NaCl type structure, β-MnS with zinc-blende type structure) used during the synthesis. Additionally a CuMn_xIn_1−xS₂ powder sample, in which Mn substitutes the M^III site, was investigated. The SQUID measurements revealed a well-distinct magnetic transition between 15 and 16 K as well as ferromagnetic-like hysteresis loops pronounced for temperatures below the transition temperature. Below this temperature a clear splitting between the zero field cooling (ZFC) and the field cooling (FC) curves indicate to the existence of a long-range magnetic ordering phenomenon. This behaviour was not found in the other samples were Mn substitutes both sites M^I as well as M^III.     

Molecular constants for the interacting upper states of the ν1, ν3, 2ν2, ν2 + ν4, and 2ν4 bands in 12CH4

In a previous paper (J.-E. Lolck and A. G. Robiette, J. Mol. Spectrosc.88, 14 (1981)) a theoretical model for the interacting upper states of the ν₁, ν₃, 2ν₂, ν₂ + ν₄, and 2ν₄ bands in methane was described. The present paper summarizes the results obtained, using this model, in a comprehensive analysis of the five bands of ¹²CH₄ through J′ = 12. Values of 80 molecular constants, of which 17 correspond to vibrationally off-diagonal operators, are reported. In addition the computed energy levels of the v₃ = 1 state are compared to the experimental ones and to the result of the previous isolated band approach.     

Anomalous Λ-doubling of the X2Π state of N Se

The rotational analysis of the A-X and A′-X systems of the ¹⁴N⁸⁰Se and ¹⁵N⁸⁰Se molecules has revealed an anomalous Λ-doubling of the X²Π state. This is attributed to an interaction between the nearly degenerate v + 1 and v levels of the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ substates. The s-uncoupling operator is shown to be responsible for the mixing. Due to the variation with r of the B rotational constant, the vibrational matrix element is non vanishing for Δv = 1. Its value obtained by a least squares fit of the observed term values is in excellent agreement with the calculated one.     

Simultaneous analysis of the ν1, ν4, 2ν2, ν2 + ν5, and 2ν5 infrared bands of 12CH3F

The Fourier-transform spectrum of CH₃F from 2800 to 3100 cm^?1, obtained by Guelachvili in Orsay at a resolution of about 0.003 cm^?1, was analyzed. The effective Hamiltonian used contained all symmetry allowed interactions up to second order in the Amat-Nielsen classification, together with selected third-order terms, amongst the set of nine vibrational basis functions represented by the states ν₁(A₁), ν₄(E), 2ν₂(A₁), ν₂ + ν₅(E), 2ν₅⁰(A₁), and 2ν₅^±2(E). A number of strong Fermi and Coriolis resonances are involved. The vibrational Hamiltonian matrix was not factorized beyond the requirements of symmetry. A total of 59 molecular parameters were refined in a simultaneous least-squares analysis to over 1500 upper-state energy levels for J ≤ 20 with a standard deviation of 0.013 cm^?1. Although the standard deviation remains an order of magnitude greater than the precision of the measurements, this work breaks new ground in the simultaneous analysis of interacting symmetric top vibrational levels, in terms of the number of interacting vibrational states and the number of parameters in the Hamiltonian.     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.     

The vibration-rotation spectrum of methinophosphide: The overtone bands 2ν1 and 2ν3, the summation bands ν1 + ν2 and ν2 + ν3, and the difference band ν1 - ν2

The vibration-rotation bands 2ν₁, 2ν₃, ν₁ + ν₂, ν₂ + ν₃, and ν₁ - ν₂ of H¹²CP were recorded and analyzed. These data were combined with previously reported results for this molecule to obtain an improved and extended set of vibrational and rotational constants. All x_ij and γ_ij were calculated except those that require data from a summation band involving ν₁ and ν₃.     

High-resolution study of some doubly excited vibrational states of PH2D: the ν1+ν2, ν2+ν5, ν2+ν3, and ν2+ν6 bands

The absorption bands ν₁+ν₂, ν₂+ν₃, and ν₂+ν₆ of PH₂D have been recorded for the first time using a high-resolution Bruker 120 HR interferometer, and rotationally analyzed. Some transitions belonging to the very weak band ν₂+ν₅ and enhanced in intensity by strong interactions with the ν₁+ν₂ band were also assigned. Sets of parameters obtained from the fit reproduce experimental line position of the bands ν₁+ν₂ and ν₂+ν₃ with about the experimental accuracy. The residuals of the ro-vibrational energies of the ν₂+ν₆ band are about 10 times larger. Reasons for the poorer reproduction of the latter data are given.