Wechselwirkung von Elektronen mit Gitterschwingungen in Ammoniumchlorid und Ammoniumbromid

Energy loss spectra of polycrystalline NH₄Cl and NH₄Br films have been studied between 10 and 400 meV using 30-keV electrons. The resolution of the spectrometer was between 4 and 10 meV, the scattering angle smaller than 1.2×10^?4 radian. Strong energy losses and gains were found near 20 meV corresponding to excitation of translational lattice vibrations wellknown from reststrahl measurements. Weaker energy losses above 100 meV are due to excitation of ammonium ion fundamentals and their interaction with torsional vibrations and, presumably, with translational lattice vibrations. In this energy loss range agreement is stated concerning the general behaviour between energy loss and infra-red absorption spectra. In the finer details, however, striking deviations occur, which must be ascribed to the different interaction mechanisms of lattice vibrations with electrons and photons, respectively.     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

The Raman spectra of NH4I at high pressures. The existence of a new phase in the ammonium halides

The Raman spectra of NH₄I and ND₄I show significant changes at higher pressures which can only be interpreted in terms of the existence of a new phase. This is not an intermediate phase occurring between phases II and IV, but is observed upon further compression of the ferro-ordered phase IV. Preliminary measurements show that the same phase transition occurs in NH₄Br and NH₄Cl, but at significantly higher pressures than the one in NH₄I.     

Two-phase region in the lambda transition of NH4Br and ND4Br

The specific volumes of NH₄Br and ND₄Br were measured with a precision dilatometer, based on hydrostatic weighing, between 160° and 300°K to exanine the existence of a two-phase region in the lambda transition. Probably NH₄Cl and ND₄Cl have analogous two-phase regions.     

Ultraviolet reflectivity of NH4Cl and NH4I in ordered and disordered phases

Near-normal incidence reflectivity spectra below 10 eV of NH₄Cl in phases II and IV and of NH₄I in phases II and III are reported. An interpretation is given by comparing these spectra with those of alkali halides. A temperature shift of the first exciton peak of NH₄I due to ordering of the crystal was found as was the case with NH₄Br. The absence of this effect in NH₄Cl strongly implies the relation to the transition II–III and the tetragonal distortion of the lattice.     

Transition energies of ND4Cl and ND4Br in the transition I⇄II

The energy of the transition I?II of ND₄Cl and ND₄Br was measured by using a direct differential calorimetric method. The results 1024 cal/mole for ND₄Cl and 847 cal/mole for ND₄Br were obtained. The accuracy was estimated to be about 2%. The approximate transition temperatures 169°C for ND₄Cl and 118°C for ND₄Br were observed.     

Photoionization cross sections: He I- and He II-photoelectron spectra of homologous oxygen and sulphur compounds

The structure of the 1₁₁→1₀₁ transition of ND₂H has been studied by means of millimetre-wave beam maser spectroscopy. Twenty-five components which result from the nitrogen, deuterium, and hydrogen hyperfine interactions have been resolved and theoretically analysed. The theory of three identical particles is discussed and used to fit the beam measer spectra of the J = K = 4 and J = K = 6 inversion transitions of ND₃ which have been reported previously. These results are compared with those of the submillimetre-wave beam maser spectrum of the J = 1 →0 transition of ND₃. By use of molecular and isotopic relations, the results of this work are critically compared with previous centimetre-wave beam maser studies of NH₃ and NH₂D.     

Realization of controllable etching for ZnO film by NH4Cl aqueous solution and its influence on optical and electrical properties

ZnO films were deposited on c-plane Al₂O₃ substrates by pulsed laser deposition. The etching treatments for as-grown ZnO films were performed in NH₄Cl aqueous solution as a function of NH₄Cl concentration and etching time. It was found that NH₄Cl solution is an appropriate candidate for ZnO wet etching because of its controllable and moderate etching rate. The influence of etching treatment on the morphology, optical and electrical properties of the ZnO films has been investigated systematically by means of X-ray diffraction, atomic force microscope, photoluminescence and Hall effect. The results indicated that the surface morphology and optical properties of the films were highly influenced by etching treatment.     

Microwave substitution structure of the amine group in Ortho-chloroaniline,C6H4CINH2

The microwave spectra of amine deuterated species of [2-³⁵Cl] and [2-³⁷-Cl]aniline, C₆H₄ClNH₂, have been observed. The rotators associated with the first two states of the amino group inversion have been assigned. A geometric structure has been calculated from the moments of inertia of all isotopic species in the ground state, indicating a small out-of-plane angle (34.5°), and a torsion around the CN bond of the NH₂ group. This deformation is explained by the formation of a hydrogen bond NH … Cl.     

Vibration-inversion-rotation spectra of ammonia: A vibration-inversion-rotation Hamiltonian for NH2D and ND2H

The model Hamiltonian developed previously for ammonia NH₃ has been used to study the vibration-inversion-rotation energy levels of the isotopic species of ammonia NH₂D and ND₂H. In this model the inversion motion is removed from the vibrational problem by allowing the molecular reference configuration to be a function of the large amplitude motion coordinate.The ground state inversion-rotation energy levels of NH₂D and ND₂H have been calculated with the use of the zeroth-order inversion-rotation Hamiltonian, and the calculated transition frequencies have been compared with the experimental data.     

Line width transitions in the deuteron magnetic resonance of polycrystalline ND4Cl,ND4Br,and ND4I

The line width of the deuteron magnetic resonance in polycrystalline ND₄Cl, ND₄Br, and ND₄I has been measured from 300°K down to 115°K. Below 200, 172, and 140°K in ND₄Cl, ND₄Br, and ND₄I, respectively, the line rapidly broadens. In addition, the I ? II transition of ND₄I causes a change of line width. The observed line widths agree with those calculated by the present writers from theVan Vleck second moment formula assuming a Gaussian line shape. For this agreement, in the phases II and III of ND₄Cl and in the phase I of ND₄I the deuteron-halogen interactions should be taken into account, whereas in the phases II and III of ND₄Br and ND₄I they should be omitted.     

Neutron diffraction study of high-pressure-induced structural changes in the ammonium halogenides ND4Br and ND4Cl

Structural changes in the deuterated ammonium halogenides ND₄Br and ND₄Cl have been studied by neutron time-of-flight diffraction up to pressures of 45 and 35 kbar, respectively. Data on the equations of state and pressure dependence of the deuterium position parameter have been obtained. A comparison with the hydrogen-containing analogs showed that isotopic substitution of deuterium for hydrogen affects only slightly the compressibility of the systems under study, although the effect is noticeable for ND₄Cl. It has been established that the order-disorder transition from the phase with random deuterium distribution (CsCl cubic structure, space group Pm3m) to the ordered phase (same structure, space group ) occurs in both compounds at the same critical value of the position parameter u=0.153±0.002, which is apparently the same for all ammonium halogenides, and, possibly, for other systems of this structural type as well. Fiz. Tverd. Tela (St. Petersburg) 40, 142–146 (January 1998)     

A new interpretation of the critical behavior in NH4Cl and ND4Cl

It is proposed that the first order transition of NH₄Cl and ND₄Cl is not located near a tricritical point but near a critical point of type 4. Good agreement between the measured and calculated values of the critical exponent β and α′ is obtained.     

On the deuteron magnetic resonance in single crystals of ND4Cl and ND4Br

The deuteron quadrupole coupling constants in ND₄Cl and ND₄Br have been measured. The results are 179.9±2.0 and 180.0±2.0 kHz, respectively. From the temperature dependence of the line width in ND₄Cl for the d. c. magnetic field along [100] the hindered rotation potential barrier of the ND₄ ⁺-ion was found to be 5.1 kcal/mole. In crystals containing moisture a narrow line component was observed, which is probably due to the formation of an eutectic solution.     

Hydrogen‐bonding interactions in fully deuterated α‐glycine at high pressures

Recent spectroscopic investigations of various amino acids report intriguing high‐pressure and low‐temperature behavior of NH₃⁺ groups and their influence on various hydrogen bonds in the system. In particular, the variation of the intensity of NH₃⁺ torsional mode at different temperatures and pressures has received much attention. We report here the first in situ Raman investigations of fully deuterated α‐glycine up to ∼20 GPa. The discontinuous changes in COO⁻ and ND₃⁺ modes across ∼3 GPa indicate subtle structural rearrangements in fully deuterated α‐glycine. The decrease in the intensity of ND₃⁺ torsional mode is found to be similar to that of undeuterated α‐glycine. The pressure‐induced stiffening of N D and CD₂ stretching modes are discussed in the context of changes in the hydrogen‐bonding interactions. Copyright © 2011 John Wiley & Sons, Ltd.     

Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)

Successive structural phase transitions of (4-ClC₆H₄NH₃)₂CuCl₄, which occur in a very narrow temperature range were reinvestigated by Fourier transform nuclear quadrupole resonance (FT NQR) measurements. The phase transitions at 275.5 and 277.0 K were confirmed. The effect of the deuteration of the ammonium end on these transitions was studied. The³⁵Cl NQR frequencies of organic cation were observed to decrease by about 4 kHz and the phase transition temperatures to decrease by about 2 K by the deuteration, suggesting that the ?NH₃ ⁺ … Cl hydrogen bond is weakened by the deuteration. The magnetic phase transition temperature of 8.6 K showed no remarkable change within experimental error by the deuteration. It was found that the magnetically ordered state is broken by the radio-frequency magnetic field of about 15–35 Oe usually employed in pulsed NQR. However, in the deuterated compound (4-ClC₆H₄ND₃)₂CuCl₄, the ordered state was found to be stabler for the usual radiofrequency power. By combining with the NQR data of (4-ClC₆H₄NH₃)₂CuBr₄ and (3,5-Cl₂C₆H₃NH₃)₂CuCl₄, the possibility is discussed of tuning the interlayer interaction between the organic cation layer and the inorganic complex anion layer by the halogen substitution in the organic cation as well as by the halogen replacement in the inorganic complex anion.     

Incommensurability and metastability problems in NH4HSeO4 and ND4DSeO4: A reinvestigation of phase diagrams

Abstract

X-ray and neutron diffraction results on NH₄HSeO₄ and ND₄DSeO₄ are reported. Direct evidence of an incommensurate phase sandwiched between the monoclinic high-temperature phase (space group B2) and the low-temperature ferroelectric lock-in phase k = ? (space group P1) has been obtained in NH₄HSeO₄. The phase situation is more complicated in ND₄DSeO₄, where an incommensurate phase is found sandwiched between the B2 phase and a lock-in phase k = ¼ and where a phase in which several modulations coexist has been discovered in between the two lock-in phases k = ¼ and k = ?. The non-equilibrium processes, also present in ND₄DSeO₄, have been identified. All these results have clarified the situation about the phase diagram.     

The 5νNH and 5νND vibrational bands of partially deuterated ammonia species

Absorption spectra of gaseous samples containing NH₂D and NHD₂ have been measured in the 11 580-11 880 and 15 280-15 610 cm⁻¹ regions, corresponding to the 5ν_ND and 5ν_NH vibrational bands, respectively. Photoacoustic spectroscopy has been utilized for the measurement. The molecular constants of NH₂D in the 5ν_ND state and NHD₂ in the 5ν_NH state have been determined from the analysis of the obtained absorption spectrum. From the comparison of the constants with those of the vibrational ground states, structural changes caused by the stretching excitations have been elucidated. The HND bond angles are decreased by these excitations. The dependence of the molecular constants on the stretching quantum number has also been derived by simple Birge-Sponer and Dunham analyses.     

Raman study of (NH4)2CuCl4·2H2O—I: Dynamics and structure in low temperature phase

We report the results of a Raman scattering study of (NH₄)₂CuCl₄2H₂O at 300, 205 and 100°K, in order to elucidate the dynamics and phase transition in this double salt. A group theoretical calculation of the symmetry vectors, in the high temperature phase (D_4h¹⁴), is made and the various modes are identified. The deuterated compound (ND₄)₂CuCl₄·2D₂O has also been investigated to help in identifying the modes involving motion of the ammonium ions and water molecules. Through a careful analysis of the spectra at 100°K, the space group in the low temperature phase has been established as D_2d³. The important consequence of this result is that this leads to parallel spatial ordering of ammonium tetrahedra in this compound in the low temperature phase.     

Rotational analysis of the ν2 band of NH2D

High-resolution diode laser spectra and medium-resolution F-T spectra of deuterated ammonia have been obtained in the 700- to 1030-cm⁻¹ region. Out of about 800 lines measured by diode laser spectroscopy, approximately 500 lines have been assigned to the ν₂ transitions of NH₂D. The parameters for the ground and ν₂ states of NH₂D have been derived by the simultaneous analysis of the infrared and microwave data. The standard deviation for the IR data is ∼8 × 10⁻⁴ cm⁻¹. It is shown that the energy levels of NH₂D in the ν₂ state are heavily perturbed by inversion-rotation interaction and that it is necessary to include higher order inversion-rotation interaction terms to obtain a satisfactory fit of the observed data.