Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

K-shell and valence shell excitations in CF4 by 2.5 keV electron impact

Energy loss spectra of 2.5 keV electrons, scattered through small angles by CF₄, have been obtained in the region of valence, carbon K- and fluorine K-shell excitations. The carbon K-shell spectrum has features which may be associated with the existence of an effective potential barrier in the CF₄ molecule.     

Carbon K-shell excitation in acetone by 2.5 keV electron impact

The energy loss spectrum of 2.5 keV electrons, scattered by gaseous acetone through small angles, has been obtained in the region of the carbon K-edges. Discrete structure observed below the ionization threshold is interpreted as arising from the promotion of a carbon K-shell electron to Rydberg orbitals. Broad peaks observed above the K-edges are associated with the simultaneous transitions of a carbon K-shell and valence shell electrons (shake-up and shake-off processes).     

Single orbital relaxations accompanying core ionization in the isoelectronic series CH4, NH3, H2O,HF and Ne

Single orbital contributions to the total relaxation energy accompanying core ionization are computed by means of non-empirical LCAO MO SCF calculations within the ΔSCF formalism for the isoelectronic series CH₄, NH₃, H₂O, HF and Ne. Individual contributions to the total relaxation energy associated with the valence levels of essentially core-like 2s character are also presented.     

Sol-gel synthesis of iron(III) oxyhydroxide nanostructured monoliths using Fe(NO3)3·9H2O/CH3CH2OH/NH4OH ternary system

Iron(III) oxyhydroxide xerogels were prepared through sol-gel technology, using iron(III) nitrate nonahydrate as precursor, ethanol as solvent and ammonium hydroxide as gelation agent. This base is used for propylene oxide substitution, which was the gelation agent in previous works. Synthesis of a gel using NH₄OH as a gelation agent is an innovative result with this type of precursor, since with metal salts the addition of a strong base commonly results in precipitation of the solid. The gel synthesis was achieved by controlling the base addition time. The dried material has a residual amount of organic impurities, in contrast with the significant amount detected in xerogels prepared using propylene oxide. The iron phase prevailing in the produced xerogels can be defined as γ-FeO(OH) (lepidocrocite), according to FTIR and Mössbauer analyses. The xerogels are formed by large clusters of well connected nanocrystallites of this phase. XRD revealed a crystalline phase retained inside the iron oxyhydroxide amorphous structure, which corresponds to NH₄NO₃ and results from the combination of NO₃⁻ and NH₄⁺ ions in solution. The produced xerogel has a promising composition to be an oxidizing composite for the energetic materials area.     

乙醇与水协同修饰Bi2WO6纳米片形貌及改善其光致发光性

通过控制前驱体中乙醇与水的体积比,采用溶剂热法得到不同形貌的Bi2WO6纳米片,探讨了Bi2WO6形貌与光致发光性能之间的关系。Bi2WO6的结晶度、纳米片的棱长以及片层间距随醇水比增大而逐渐提高,当醇水比为1∶1时,Bi2WO6纳米片的棱长、片层间距和比表面积（BET）最大,表现出优异的光致发光性能;而在醇水比大于1∶1时,纳米片的棱长、片层间距和BET随之降低,光致发光性能继而减弱。以上表明醇水比为1∶1时,复配乙醇与水协同修饰Bi2WO6纳米片形貌的效果最佳,BET最大,从而促进其光致发光性能的改善。     

Birefringence,X-ray and neutron diffraction measurements on the structural phase transitions of (CH3NH3)2 MnCl4 and (CH3NH3)2FeCl4

We used optical birefringence, X-ray and neutron diffraction methods with single crystals to study the structural phase transitions of the perowskite-type layer structures of (CH₃NH₃)₂MeCl₄ with Me=Mn, Fe. The Mn-compound shows the following structural transitions at 394 K — a continuous order-disorder phase transition from tetragonal symmetry $\text{I4}\text{mmm}$ to orthorhombic space group Abma (Cmca in reference 10); at 257 K — a discontinuous transition to a second tetragonal modification; at 95 K — a discontinuous transition to a monoclinic phase. For the Fe-compound the corresponding transition temperatures are 328 K and 231 K, respectively. A low temperature monoclinic phase could not be observed. The lattice parameters of the different modifications were determined as a function of temperature. The temperature dependent course of the order parameter has been investigated for the order—disorder transition. For both compounds, all the methods used gave the same value for the critical exponent of β = 0.315.     

Carbon K-shell excitation of C2H2, C2H4, C2H6 and C6H6 by 2.5 keV electron impact

Energy loss spectra of 2.5 keV electrons in the region of the carbon K-edge in C₂H₂, C₂H₄, C₂H₆ and C₆H₆ are report     

Structural characterization,thermal, vibrational properties and molecular motions in perovskite-type diaminopropanetetrachlorocadmate NH3(CH2)3NH3CdCl4 crystal

The work presents a detailed analysis of the sequencing of the structural phase transitions in NH₃(CH₂)₃NH₃CdCl₄ crystal by differential scanning calorimetry (DSC), X-ray, infrared, far infrared and Raman spectroscopy. DSC studies have shown that in analyzed crystal occurring one reversible continuous phase transition at 375/374 K (on heating/cooling). Observed in Nujol and Fluorolube mulls in the wide temperature range between 296 K and 413 K spectral changes through the structural phase transition can be attributed to an onset of motion of cations. An assignment of some bands due to internal modes has been also proposed.     

Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

Aimantation a basse temperature de deux sels ferromagnetiques uniaxes. Cu(NH4)2Br4, 2H2O ET CuRb2Br4, 2H2O

The low temperature spontaneous magnetization of the spin 1/2 b.c.c. ferromagnet has been computed using the self-consistently renormalized spin-wave theory of Bloch, taking into account weakly anisotropic exchange. A good agreement with our experimental data in Cu(NH₄)₂Br₄, 2H₂O and CuRb₂Br₄, 2H₂O is observed for 0 < T/T_{c < 0.5}, using the following anisotropy fields at 0°K: (293 ± 25) oe in Cu(NH₄)₂Br₄, 2H₂O and (300 ± 25)oe in CuRb₂Br₄, 2H₂O.     

Magnetic resonances in (CH3NH3)2MnCl4

We have studied the magnetic excitations of (CH₃NH₃)₂MnCl₄ in the antiferromagnetic and in the spin-flop regimes by means of magnetic resonance in the millimeter range (60–100 GHz). Rather odd line shapes of the resonance absorption line for narrow lines are explained as interference effects between the resonant and the non-resonant circular wave in the sample. For the antiferromagnetic resonance (AFMR) and for the paramagnetic resonance (EPR, above the Néel temperature), we have also studied the line width as a function of temperature.     

Elucidating surface properties of dry-etched ZnO using H2/CH4 and H2/CH4/Ar plasma

This paper reports a study of reactive ion etching (RIE) of n-ZnO in H₂/CH₄ and H₂/CH₄/Ar gas mixtures. Variables in the experiment were gas flow ratios, radio-frequency (rf) plasma power, and total pressure. Structural and electrical parameters of the etched surfaces and films were determined. Both the highest surface roughness and highest etching rate of ZnO films were obtained with a maximum rf power of 300 W, but at different gas flow ratios and working pressures. These results were expected because increasing the rf power increased the bond-breaking efficiency of ZnO. The highest degree of surface roughness was a result of pure physical etching by H₂ gas without mixed CH₄ gas. The highest etching rate was obtained from physical etching of H₂/Ar species associated with chemical reaction of CH₄ species. Additionally, the H₂/CH₄/Ar plasma treatment drastically decreased the specific contact and sheet resistance of the ZnO films. These results indicated that etching the ZnO film had roughened the surface and reduced its resistivity to ohmic contact, supporting the application of a roughened transparent contact layer (TCL) in light-emitting diodes (LEDs).     

Synthesis and crystal structure of [3,5-(CH3)2C6H3NH3]4P4O12·3H2O

Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH₃)₂C₆H₃NH₃]₄P₄O₁₂·3H₂O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)ų. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P₄O₁₂ ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described.     

Absolute Raman intensities of CH4, CH3D,CH2D2, CHD3, and CD4

Measurements of the absolute vibrational Raman intensities and depolarization ratios for the fundamental and some overtone and combination bands of CH₄, CH₃D, CH₂D₂, CHD₃, and CD₄ are reported. Experimental aspects of these measurements are discussed. The experimental data conform satisfactorily to all isotope intensity sum rules. The measured intensities and depolarization ratios, together with the vibrational potential function for CH₄, make possible the calculation of the four independent parameters of the isotopic invariant quantities $\text{α}{}^{\mathrm{S}}\text{= |}\text{?α}\text{?S}\text{|}$. The results deduced from these agree with all 36 experimentally observed values. Values of electro-optical parameters for the CH bond are calculated and discussed.     

K- and LII,III-Shell excitations in CS2 and COS by 2.5 keV electron impact

Energy loss spectra of 2.5 keV electrons, scattered by CS₂ and COS through small angles, have been studied in the regions of the respective oxygen K, carbon K and sulfur L_{II, III}(2p) edges. The carbon and oxygen K-shell spectra are dominated by the first discrete transition similar to the K-shell spectra of the “isoelectronic” molecules CO₂ and N₂O. However, the carbon K-shell spectra of CS₂ and COS have features which may indicate the possible existence of an effective potential barrier in these molecules.     

Line Broadening and Mixing in NH3 Inversion Doublets Perturbed by NH3, He, Ar, and H2

Measurement of absorption by pure ammonia and NH₃–(H₂, He, and Ar) mixtures in the P branch of the ν₄ band at room temperature have been made with a high-resolution Fourier transform spectrometer. Least squares fits of the spectra using different techniques are used for the analysis of the evolution with pressure of the absorption shape for a number of ^PP inversion doublets. Intensities, half-widths, and line-coupling parameters are determined, demonstrating the great importance of line-mixing effects. The results are compared with values calculated using a semiclassical model. The latter explains most of the features of the line-broadening and the J and K dependencies of line-coupling for pure NH₃, whereas poorer results are obtained for line-mixing in mixtures. The most striking and original result is the very large amount of coupling between the symmetric and antisymmetric components, which can reach up to 80% of the width in the case of pure NH₃. Also remarkable is the very strong influence of the rotational quantum number K.     

Structure and magnetic properties of a new single-molecule magnet [Mn11Fe1O12 (CH3COO)16(H2O)4].2CH3COOH.4H2O

A new single-molecule magnet [Mn₁₁Fe₁O₁₂ (CH₃COO)₁₆(H₂O)₄]?2CH₃COOH?4H₂O (Mn₁₁Fe₁) has been synthesized.The structure has been studied by the single crystal x-ray diffraction. The difference of Jahn--Teller distortion between Fe³⁺ and Mn³⁺ ion reveals that Fe³⁺ ion substitutes for Mn³⁺ ion on the Mn(3) sites in the Mn₁₂ skeleton. The temperature dependence of the magnetization gives a blocking temperature T_B=1.9K for Mn₁₁Fe₁. Based on the magnetization process analysis of the crystal at T=2K, we suggest that Mn₁₁Fe₁ has the ground state with a total spin S= 11/2.     

Vibrational study of H3OUO2PO4·3 H2O (HUP) and related compounds. Phase transitions and conductivity mechanism: Part II,H3OUO2PO4·3 H2O

Infrared and Raman spectra of polycrystalline H₃OUO₂PO₄·3 H₂O (HUP) and its D and P¹⁸O₄ derivatives, in the form of dense transparent disks and wet powder, have been investigated at various temperatures in the 100–300 K region. The bands due to framework vibrations are similar to those of KUP, whereas those for the protonic species are different. OH stretching and bending bands of the oxonium ion have been identified at 2920, 1740 and 1160 cm^?1 in the low-temperature spectrum of HUP. Differential scanning calorimetry (DSC) and infrared (IR) intensity investigations show a phase transition between 274 and 260 K. The mechanism of the phase transition consists, as in the case of KUP, of ordering of the protonic species, which induces ordering of PO₄ tetrahedra. The ordering can be influenced by excess water content, stacking faults and stress (ferroelastic behaviour is evidenced). The conductivity mechanism in HUP is discussed.