First observation of ferromagnetism and ferromagnetic domains in a liquid metal

80 Pd₂₀ alloy below the Curie temperature T_C(l)=1257 K of the liquid state. The magnetization of the undercooled liquid sample has been measured as a function of temperature using a modified Faraday balance. Below T_C(l), the magnetization of the liquid metal shows a plateau in the weak external field of μ₀H_z=5.6 mT. The effect is comparable to the behaviour of the corresponding solid phase, indicating the onset of spontaneous magnetization with ferromagnetic domains. T_C(l) is about 20 K lower than the Curie temperature of the solid phase T_C(s). Received: 24 February 1997/Accepted: 16 May 1997     

Sensitization of luminescence of antimony(III) in complexes with 6-methylquinoline in the spectral region of the <Emphasis Type="Italic">A</Emphasis> band

The luminescence properties of complexes of antimony (III) halides with 6-methylquinoline: (C₁₀H₉NH)₄Sb₂Cl₁₀ (I), (C₁₀H₉NH)₃SbBr₆ (II), and (C₁₀H₉NH)₄Sb₂I₁₀ (III) are studied. From analysis of data obtained by UV, photoelectron, and luminescence spectroscopy, it is concluded that the decrease in the energy gap between the highest occupied and lowest unoccupied molecular orbitals of the 6-methylquinoline molecules and antimony (III) halides is responsible for quenching of the luminescence of the 6-methylquinolinium cations and for occurrence of intrinsic luminescence of the antimony (III) ions in going from complex I to complexes II and III.     

Superconductivity in the graphite-potassium intercalation compound C8K

Superconducting properties of pseudo-single crystals of C₈K were investigated by low frequency a.c. magnetic susceptibility and electrical resistivity measurements. The measured values of T_c were between 128 and 198 mK for 13 samples. Measurements of the superconducting transition in a magnetic field revealed a remarkable anisotropy, such that if θ is defined as the angle between the applied magnetic field and the layer plane, type II superconductivity was observed for 0° ≦ ∣ θ ∣ ? 25° and type I superconductivity for 25° ? ∣ θ ∣≦ 90°. The angular dependences of H_c2 and H_c3 were fairly well-explained by the effective mass model.     

Adsorption of ethylene on clean and oxygen precovered Cu(110) surfaces

UV photoemission spectroscopy (UPS) with He I and He II radiation is used to study the interaction of C₂H₄ with clean and oxygen precovered Cu(110) surfaces at 90 K. On the clean surface only-bonding of the C₂H₄ molecules is observed whereas preadsorbed oxygen causes a second molecular orbital to be involved in the chemisorption. This result is consistent with the differing behaviour of the work function change during thermal desorption of C₂H₄.     

Relative intensities in x-ray photoelectron spectra. Part VI. The spectra of He(I), He(II), Y Mζ and Zr Mζ

The 2s- and 2p-electron photoionization cross-sections at photon energies up to 190 eV have been calculated, using the RPAE method for averaged configurations of the C, N, O and Ne atoms. The RPAE method ensures a more accurate relation between the cross-sections, 2s/2p, than that obtained using the Hartree—Fock method. Within the framework of the Gelius—Siegbahn model, but with the use of theoretical atomic cross-sections, we have calculated the photoionization cross-sections for He(I), He(II), Y Mζ, Zr Mζ for CH₄, C₂H₆, C₃H₈, C₂H₄, C₂H₂, NH₃, H₂O, CN^?, N₂, CO, CO₂, N₂O and NO₂^? molecules. For CO, N₂, CO₂, N₂O and H₂O molecules, a comparison is made between the theoretical and experimental cross-sections for hν < 60 eV. The calculated absolute and relative values of the molecular-orbital cross-sections are in reasonable agreement with experiment, especially at hν ? 40 eV. The calculations correctly reproduce the change in intensities under the transition He(I) → He(II). We have shown that our calculations have a significant advantage over those performed using the PW and OPW approximations. It is shown for NO, N₂, CO, H₂O, CH₄, NH₃ and N₂O molecules that the total photoionization cross-section calculated taking into account the real structure of the molecular orbitals is in better agreement with the experimental photoabsorption cross-section than is the sum of the cross-sections for the atoms in a molecule.     

A study of molecular reorientation in a series of liquid n-alkanes using light-scattering spectroscopy

The spectra of the depolarized (VH) light scattered from the n-alkanes C₆H₁₄, C₈H₁₈, C₁₀H₂₂, C₁₂H₂₆, C₁₄H₃₀, C₁₅H₃₂ and C₁₆H₃₄ have been measured using a high resolution piezo-electrically scanned Fabry-Perot interferometer. The values of the molecular relaxation times τ _s derived from the spectra are compared with relaxation times τ _f derived from flow birefringence. The experimental results are discussed in terms of a phenomenological activation energy and also in terms of the coupling between the molecular reorientation and the hydrodynamic shear modes, allowing estimates of the strength of the coupling between these modes to be made.     

The geometry and forcefield of acetylene

The variational method has been used to determine the geometry and ground state potential surface of acetylene. All the parameters were refined through a least-squares fit to J = 0, 1 levels for C₂H₂ and C₂D₂. A new program was written to evaluate the rovibrational energy levels; in particular, primitive basis sets were developed for all values of J taking into account the singularity for linear geometries. Thus Σ, II, δ states can be refined. The full theory for tetraatomic linear molecules is presented. In this refinement 150 observed levels were used as data, below 10 000cm^?1. The geometry was refined and gives R_e(CC) = 1.2028 Å, R_e(CH) = 1.0618 Å, to be compared with the best experimentally derived values of 1.2027 ± 0.0005 Å, 1.062 ± 0.001 Å, respectively. The zero point energies are 5771.1cm^?1 for C₂H₂ and 4571.1cm^?1 for C₂D₂.     

The universality of the electron spin relaxation in C60 mono radical anion salts: EPR studies of the model system [P(C6H5)4]2C60X

The C₆₀ radical anion salts [P(C₆H₅)₄]₂C₆₀X (X=Cl, Br, I) are grown via electrocrystallization and used as a model system to study the electron spin and nuclear spin dynamics as well as the molecular dynamics of C₆₀ mono anions in the solid state, which obey universal laws. It is shown that [P(C₆H₅)₄]₂C₆₀X is an exception among the fullerides, since the temperature dependence of the JT distortion, predicted for ionic C₆₀, can be deduced.     

Synthesis,spectroscopic and structural characterisation of two p-nitrobenzamide compounds: experimental and DFT study

The title molecules, N-(1,5-dimethyl-3-oxo-2-phenyl-1H-3-(2H)-pyrazolyl)4-nitrobenzamide (C₁₈H₁₆N₄O₄·H₂O) (I) and 2,2-dimethyl-3-(4-nitrobenzoyl)-5-(phenylamino)-2,3-dihydro-1,3,4-thiyadiazole (C₁₇H₁₆N₄O₃S) (II), were prepared and characterised by ¹H NMR, ¹³C NMR, infrared spectroscopy (IR) and structural X-ray diffraction (XRD) techniques. The molecular geometries, vibrational frequencies of the title compounds in the ground state have been calculated by using the density functional theory (DFT) method with 6-31G(d) basis set, and compared with the experimental data. The calculated results showed that the optimised geometries from the DFT method agree with the X-ray structures well for both compounds. Theoretical calculations of harmonic vibration frequencies are in good agreement with experimental results. To determine conformational flexibility, the molecular energy profiles of the title compounds were obtained. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and thermodynamic properties of the title compounds were investigated by theoretical calculations.     

The Raman and Infrared Spectra and Structures of Ethyl Chloride,Bromide and Iodide

The Raman, infrared and proton NMR spectra of the liquid molecules, C₂H₅-X(X[dbnd]Cl, Br, I) have been recorded. And the molecular structures have been studied on the basis of these spectra. Consequently a non-rigid structure in which a CH₂ group rotates freely with respect to the three hydrogen atoms of CH₃ group is established.     

An electrochemical sensing platform based on a new Cd(II)-containing ionic liquid for the determination of trichloroacetic acid and bromate

The present work reports on the synthesis, characterization and performance of a new metal-containing ionic liquid [(C₃H₇)₂-bim]₂[CdCl₄] (bim = benzimidazole) as an electrocatalyst for trichloroacetic acid (TCA) and bromate reduction. The structure of Cd(II)-containing ionic liquid (Cd-IL) was characterized by X-ray crystallography, IR spectroscopy, and elemental analysis. The molecular structure contains two independent cations of 1,3-dipropyl-benzimidazolium and one anion of CdCl₄²⁻. The cadmium atom has a tetrahedral geometry by coordinating to four chlorine atoms. The melting point of Cd-IL is 73 °C. Electrochemical properties of the Cd-IL have been investigated by preparing bulk-modified carbon paste electrode, and Cd-IL is used as a binder and an electrocatalyst. This modified electrode has good electrocatalytic activity toward reduction of TCA and bromate. The detection limit and the sensitivity are 0.01 μM and 102.72 μA μM⁻¹ for trichloroacetic acid detection and 0.003 μM and 496.15 μA μM⁻¹ for bromate detection. This work demonstrates that the Cd-IL may become a new kind of functional material in constructing chemicals and biosensors.     

Anomalies in the Magnetic Susceptibility in the Second-Order Phase Transitions beyond the Curie Point

Taking into account the inexhaustible interest in studying the peculiarities of physical properties in the neighborhood of phase transitions and the growth of experimental investigations of cobalt fluoride, we have studied the peculiarities of magnetic susceptibility in the vicinity of the critical field H_C at which cobalt fluoride performs the second-order phase transition from the antiferromagnetic phase to the angular phase. It is discovered that in the magnetic field H ‖ C₄, the magnetic susceptibility becomes infinite at H → H_C. It is shown that as the magnetic field direction deviates from the C₄ axis, the magnetic susceptibility in the critical field H_C proves to be finite. It is also shown that the change in the magnetic susceptibility with the change in the magnetic field considerably decreases at extremely insignificant deviations of the field H from the C₄ axis. Since the calculations are performed in terms of the Landau theory of phase transitions, we pay attention to the similarity and difference between the obtained results and those in the vicinity of the Curie point obtained by using the Landau theory of phase transitions.     

Specific heat related to the Raman frequency shifts for the rotatory mode in ammonia solid I close to the melting point

This study gives an evidence for the validity of our spectroscopic modification of the Pippard relation as applied to ammonia solid I close to the melting point. We use our calculated frequencies for the rotatory lattice (librational) mode in ammonia solid I for the pressures of 0, 1.93 and 3.07 kbars. We obtain that the specific heat C_p varies linearly with the frequency shifts 1/ν(∂ν/∂T)_p for this Raman mode at those pressures studied in this crystalline system. Our values of the slope dP_m/dT that we deduced from the linear plots, are not in satisfactory agreement with the experimental values in ammonia solid I near the melting point.     

Nuclear magnetic resonance and transferred hyperfine interaction study of the crystallographically inequivalent Cs(I) and Cs(II) in a Cs2CuCl4 single crystal

¹³³Cs (I=7/2) nuclear magnetic resonance in a Cs₂CuCl₄ single crystal grown by using the slow evaporation method was measured in its three mutually perpendicular crystal planes. The ¹³³Cs resonances of two different groups with two crystallographically inequivalent cesium nuclei, Cs(I) and Cs(II), in the unit cell were recorded. The transferred hyperfine fields for Cs(I) and Cs(II) calculated from the paramagnetic shift and the molecular susceptibility measurements could be expressed by the linear equation H_hf=AT+B. The angular dependence of the ¹³³Cs nuclear magnetic resonance spectra showed that the Cs(I) and the Cs(II) nuclei had different values for the quadrupole coupling constant. The electric field gradient tensors of Cs(I) and Cs(II) were symmetric, and the orientations of their principal axes did not coincide. The Cs(I) ion surrounded by 11 chlorine ions had a small quadrupole parameter, a smaller charge distribution, and a small value for the transferred hyperfine field. However, the Cs(II) ion surrounded by nine chlorine ions had a larger quadrupole parameter, a larger charge distribution, and a larger value for the transferred hyperfine field.     

Mechanisms of inelastic scattering of low-energy protons by C6H6, C60, C6F12, and C60F48 molecules

The mechanisms of inelastic scattering of low-energy protons with a kinetic energy of 2–7 eV by C₆H₆, C₆F₁₂, C₆₀, and C₆₀F₄₈ molecules are studied using the methods of quantum chemistry and nonempirical molecular dynamics. It is shown that, for the C₆H₆ + proton and C₆₀ + proton systems, starting from a distance of 6 Å from the carbon skeleton, the electronic charge transfer from the aromatic molecule to H⁺ occurs with a probability close to unity and transforms the H⁺ ion into a hydrogen atom and the neutral C₆H₆ and C₆₀ molecules into cation radicals. The mechanism of interaction of low-energy protons with C₆F₁₂ and C₆₀F₄₈ molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the noncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized, on the one hand, on the positively charged hydrogen ion and, on the other hand, on the C₆F₁₂ and C₆₀F₄₈ molecules. As a result, the neutral molecule + proton state becomes the ground state. In turn, this inversion makes the electronic charge transfer energetically unfavorable. Quantum-chemical and molecular-dynamics calculations on different levels of theory showed that, for fluorine derivatives of some aromatic structures (C₆F₁₂, C₆₀F₄₈), the barriers to proton penetration through carbon hexagons are two to four times lower than for the corresponding parent systems (C₆H₆, C₆₀). This effect is explained by the absence of active π-electrons in the case of fluorinated molecules.     

Quantum entanglement in nitrosyl iron complexes

Recent magnetic susceptibility measurements for polycrystalline samples of binuclear nitrosyl iron complexes, [Fe₂(C₃H₃N₂S)₂(NO)₄] (I) and [Fe₂(SC₃H₅N₂)₂(NO)₄] (II), suggest that quantum-mechanical entanglement of the spin degrees of freedom exists in these compounds. Entanglement E exists below the temperature T _E that we have estimated for complexes I and II to be 80–90 and 110–120 K, respectively. Using an expression of entanglement in terms of magnetic susceptibility for a Heisenberg dimer, we find the temperature dependence of the entanglement for complex II. Having arisen at the temperature T _E , the entanglement increases monotonically with decreasing temperature and reaches 90–95% in this complex at T = 25 K, when the side effects are still small.     

Step-Wise Concentration Influence of Fullerenes C60 and C70 on the Various Parameters of Condensed Systems

A step-wise changing concept is developed of the influence of fullerenes C₆₀and C₇₀ on various properties of condensed systems, liquid, and solid. In this, Part I is considered the step-wise character for three parameters: (1) the density of solutions; (2) the boiling points of solutions, and (3) the coefficient of the surface tension of solutions. The sharp drop of the density of solutions at very small fullerene concentrations is pointed out and considered. A step change in the coefficients of the surface tension of fullerene solutions with concentration were determined and are discussed. In Part II, to follow, the influence of fullerene concentrations on the freezing and melting of solutions will be considered.     

Quasi-one-dimensional quantum spin liquid in the Cu(C<Subscript>4</Subscript>H<Subscript>4</Subscript>N<Subscript>2</Subscript>)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> insulator

We analyze measurements of the magnetization, differential susceptibility and specific heat of quasi-onedimensional insulator Cu(C₄H₄N₂)(NO₃)₂ (CuPzN) subjected to magnetic fields. We show that the thermodynamic properties are defined by quantum spin liquid formed with spinons, with the magnetic field tuning the insulator CuPzN towards quantum critical point related to fermion condensation quantum phase transition (FCQPT) at which the spinon effective mass diverges kinematically. We show that the FCQPT concept permits to reveal and explain the scaling behavior of thermodynamic characteristics. For the first time, we construct the schematic T–H (temperature-magnetic field) phase diagram of CuPzN that contains Landau–Fermi-liquid, crossover and non-Fermi liquid parts, thus resembling that of heavy-fermion compounds.     

EPR spectra of aerosol particles formed by pyrolysis of C<Subscript>3</Subscript>H<Subscript>8</Subscript> plus Ar and C<Subscript>3</Subscript>H<Subscript>8</Subscript> plus Fe(CO)<Subscript>5</Subscript> plus Ar mixtures in a flow reactor

The paper is devoted to electron paramagnetic resonance investigation of nanoparticles and aggregates of nanoparticles formed by pyrolysis of propane as well as a mixture of propane and iron pentacarbonyl. The measurement showed that the pyrolysis of the C₃H₈ plus Ar mixture results in the formation of a carbonaceous phase (phase I), which is quite different from that formed by the C₃H₈ plus Fe(CO)₅ plus Ar mixture (phase II). In phase I there is a strong oxygen effect for as-prepared samples; 75% of spins are accessible to the environmental gas via the interconnected system of microvoids and microchannels. In phase II there was a weak oxygen effect for the as-prepared samples. However, after exposition of phase II to air for 160 h, the properties of phase II have become about the same as that of phase I. A strong oxygen effect was observed for the air-exposed phase II. The line width for phase II increases monotonically with the iron content in the sample. This increase is probably related to the dipole-dipole interactions between the radical centers and the iron atoms distributed throughout the carbon matrix.     

Photoelectron spectroscopic and thermodynamic studies of the free surface of benzyl alcohol

He(I) photoelectron spectra of the liquid surface and the vapour of benzyl alcohol (C₆H₅CH₂OH) are reported. The gas-phase spectrum resembles that of benzene except that between the 1e_1g(π) and the 3e_2g benzenoid bands there is an additional peak in benzyl alcohol at 10.69 eV. In the spectrum of the liquid the additional peak is either absent or of much reduced intensity and this, together with consideration of the spectra of related molecules, leads to its assignment as the ionization of a “lone pair” orbital. In the condensed phase the lone pair electrons become involved in hydrogen bonding. Considerations of the excess energy and entropy of the surface of liquid benzyl alcohol point to a surface in which the hydrogen bonds are not broken, in agreement with the spectroscopic result.