Refinement of hydrogen positions in Phase II of β-LiNH4SO4

The atomic positions and thermal parameters of the crystal structure for phase II of β-LiNH₄SO₄ are determined from single crystal neutron diffraction data at room temperature to refine N-H bond lengths for ammonium ions. The neutron data are collected using an E5 diffractometer in BENSC (HMI, Berlin, Germany). Atomic positions and thermal parameters are determined by the least-squares method up to R = 0.072 and wR = 0.057. It is shown that an ammonium ion polyhedron is the regular tetrahedron. The text was submitted by the authors in English.     

Refinement of the (NH4)3H(SO4)2 crystal structure: II. X-ray and neutron single-crystal diffraction from phase II at room temperature

The crystal of (NH₄)₃H(SO₄)₂ is of special interest due to the possible influence of ammonium ion on the series of phase transitions: I↔II↔ III↔IV↔V↔VII. Earlier, the x-ray single-crystal diffraction study of phase II of the (NH₄)₃H(SO₄)₂ crystal showed that the crystal structure of this compound had two crystallographically independent groups of the ammonium ions NH₄(1) and NH₄(2) but orientational positions of these ammonium ions were not determined exactly. The refinement of the NH₄(1) and NH₄(2) orientational positions in phase II was carried out by the x-ray and neutron single-crystal diffraction study. The analysis of difference Fourier maps of electron charge density and nuclear density suggested the possibility of disordering of NH₄(2) ammonium ions. The text was submitted by the authors in English.     

Neutron diffraction study of ammonium tartrate (NH4)2C4H4O6

A neutron diffraction study of ammonium tartrate has been carried out. Using the diffractometer in symmetrical setting, intensities of 750 reflections have been measured. The positions of all the hydrogen atoms have been determined. A good agreement is noticed between the present neutron and the earlier x-ray heavy atom parameters. The tartrate ion consists of two nearly identical planar halves, with an interplanar angle of 62°. Tre structure is stabilized by a net-work of hydrogen bonds. Details of hydrogen bonding and the ammonium ions environment are discussed.     

Investigation of ammonium sites in NH4NbWO6ND4NbWO6-ceramics by neutron powder diffraction

High resolution neutron powder diffraction data of NH₄NbWO₆-space group Fd3m, collected in the temperature range between 300 K and 523 K, were analysed by Rietveld refinement. The results of these refinements showed that the ammonium ions occupy 8b positions (site symmetry 43m). The hydrogens are aligned towards the nearest oxygens, indicating the possibility of weak hydrogen bonding between the ammonium group and the framework. The data are likely to suggest a Grotthus-type of proton conduction mechanism, similar to NH₄TaWO₆, which we reported previously.     

Single crystal diffraction with X-rays and neutrons: High quality at high pressure?

Abstract

Single crystal X-ray and neutron diffraction is essential for determining occupancies, positional as well as static and dynamic displacement parameters in crystalline matter by measuring Bragg, satellite or diffuse reflections. In our contribution a new low-temperature high pressure cell for neutron single crystal diffraction will be presented. It is designed to operate from a few K to ambient temperature in “orange” cryostats at pressures up to at least 3 GPa. We will present first neutron diffraction results obtained at E4/HMI Berlin and discuss the quality of the data and the significance of the results. A software package has been written (as a part of the PROMETHEUS system), which deals with the data reduction for both X-ray and neutron high pressure cell single crystal data. Likewise a data collection program has been developed for single crystal data collection on four-circle diffractometers using Merrill-Bassett cells. A series of single crystal experiments on H₂O and D₂O ice VI and KDP (KH₂PO₄) show that results of very high quality can be obtained routinely including even higher order terms in the atomic displacement parameters.     

Structure determination of Ls-threonine by neutron diffraction

The structure of the aminoacid, L_s-threonine [NH ₃ ⁺ CH(CHOHCH₃)COO^?], space groupP2₁2₁2₁,a=13.630(5),b=7.753(1),c=5.162(2) Å,z=4, has been determined from neutron diffraction data using direct methods. The intensities of 1148 neutron Bragg reflections were measured from a single crystal. The structural parameters were refined by the method of least squares using anisotropic temperature factors. The finalR(F ²) is 0.068. The structure was also refined from the x-ray data of Shoemakeret al (1950J. Am. Chem. Soc. 72 2328); there is good agreement between the two sets of heavy atom parameters. The parameters of hydrogen atoms are of course more precisely determined in our neutron study. The molecular conformation and the hydrogen bonding scheme are discussed. Weighted average values of bond distances and angles from 14 aminoacid structures with ionized carboxylic groups studied by neutron diffraction at Brookheven and Trombay are also presented.     

High-pressure neutron diffraction studies at LANSCE

The development of neutron diffraction under extreme pressure (P) and temperature (T) conditions is highly valuable to condensed matter physics, crystal chemistry, materials science, and earth and planetary sciences. We have incorporated a 500-ton press TAP-98 into the HiPPO diffractometer at the Los Alamos Neutron Science Center (LANSCE) to conduct in situ high-P–T neutron diffraction experiments. We have developed a large gem-crystal anvil cell, ZAP, to conduct neutron diffraction experiments at high P. The ZAP cell can be used to integrate multiple experimental techniques such as neutron diffraction, laser spectroscopy, and ultrasonic interferometery. More recently, we have developed high-P low-T gas/liquid cells in conjunction with neutron diffraction. These techniques enable in situ and real-time examination of gas uptake/release processes and allow accurate, time-dependent determination of changes in crystal structure and related reaction kinetics. We have successfully used these techniques to study the equations of state, structural phase transitions, and thermo-mechanical properties of metals, ceramics, and minerals. We have conducted researches on the formation/decomposition kinetics of methane, CO₂ and hydrogen hydrate clathrates, and hydrogen/CO₂ adsorption of inclusion compounds such as metal–organic frameworks (MOFs). The aim of our research is to accurately map out phase relations and determine structural parameters (lattice constants, atomic positions, atomic thermal parameters, bond lengths, bond angles, etc.) in the P–T–X space. We are developing further high-P–T technology with a new 2000-ton press, TAPLUS-2000, and a ZIA (Deformation-DIA type) cubic anvil package to routinely achieve pressures up to 20 GPa and temperatures up to 2000 K. The design of a dedicated high-P neutron beamline, LAPTRON, is also underway for simultaneous high-P–T neutron diffraction, ultrasonic, calorimetry, radiography, and tomography studies. Studies based on high-pressure neutron diffraction are important for multidisciplinary sciences, particularly for theoretical/computational modeling/simulations.     

K2H(IO3)2Cl单晶中子衍射结构分析

利用中子四圆衍射仪收集了K₂H(IO₃)₂Cl单晶的衍射数据共481个,其中独立衍射351个。利用SHELX程序做了Fourier合成及差值Fourrer合成,并用ORXFLS4程序做了最小二乘法修正(其中包括各向同性及各向异性消光修正),R因子达到3.3％,确定了结构中氢原子的位置,肯定了氢键的存在。 关键词：     

Vibrational spectra of the ammonia halides NH4I and NH4F at high pressures

The vibrational spectra of ammonium iodide NH₄I at pressures up to 4.1 GPa and ammonium fluoride NH₄F at pressures up to 4.7 GPa were investigated by inelastic incoherent neutron scattering. The pressure dependences of the transverse optical translational and librational modes were obtained. The behavior of the rotational potential barrier for the ammonium ion as a function of the lattice parameter for disordered and ordered cubic phases of ammonium halides with CsCl type structure were calculated. The results obtained confirm that the transition from an orientationally disordered cubic phase into an ordered cubic phase in ammonium halides occurs at close critical values of the positional parameter of hydrogen (deuterium).     

Structural differences between single crystal and polycrystalline UBe13

We report on observations of structural and chemical differences between samples of UBe₁₃ that were synthesised using two different methods. Unexplained discrepancies in properties between samples with differing synthesis had previously been found in this heavy fermion superconductor. A polycrystalline UBe₁₃ sample was made by arc-melting the constituents. Single crystals were grown using an aluminium flux and had a consistently slightly larger lattice parameter than the polycrystals, which merited further study. Neutron diffraction data were collected at the Lujan Center at LANSCE on the HIPPO diffractometer. Aluminium was detected by inductively coupled plasma mass spectrometry (ICP-MS) in the flux-grown single crystal (0.803 wt%), and small amounts (~0.2 wt%) of thorium were detected in the UBe₁₃ polycrystalline sample. In order to probe the implications of the presence of Al, calculations by spin-polarised DFT-GGA+U show that the incorporation of Al onto the 96i site (the lowest symmetry site in the structure) is energetically more favourable than on other sites. In general, the trends calculated by DFT for bond lengths and lattice parameter increases are consistent with bond lengths experimentally observed by neutron diffraction, but specific percentage changes with aluminium incorporation may be obscured by the unexpected thorium in the polycrystalline sample. The aggregate of our initial observations suggests that incorporation of aluminium from the flux into single crystal UBe₁₃ is significant.     

Cu-Zn disorder in Cu2ZnGeSe4: A complementary neutron diffraction and Raman spectroscopy study

The crystal structure of the quaternary compound semiconductor Cu₂ZnGeSe₄ (CZGSe) was investigated by the complementary use of neutron diffraction, and Raman spectroscopy. The powder sample, which resulting from wavelength dispersive X-ray spectroscopy (WDX) turned out to be single phase Cu-rich CZGSe, was synthesized by solid state reaction of the pure elements in an evacuated silica tube at 700 °C. Raman spectroscopy confirmed the homogeneity and phase purity of the sample, in addition, the kesterite type structure was suggested. Rietveld analysis of the neutron diffraction data confirmed that the compound crystallizes in the tetragonal kesterite type structure. The refined site occupancy factors were used to determine the average neutron scattering lengths of the cation sites, giving insights into cation distribution and finally point defect types. Thus it has been shown, that additional to the Cu_Zn-Zn_Cu anti-site defects in the lattice planes at z=¼ and ¾ (Cu-Zn disorder) also the off-stoichiometry type related point defects like Cu_i and Cu_Zn occur in Cu-rich CZGSe.     

Crystal field effects in RERh4B4 compounds (RE = rare earth)

By analysis of a large body of available data, crystal field parameters have been obtained for compounds in the series RERh₄B₄ (RE = rare-earth). These parameters have then been used to calculate properties related to the electronic and magnetic properties of such compounds, and it is shown that a substantial unification of current information is obtained for properties including bulk magnetization (polycrystalline and single crystal), magnetic susceptibility, magnetic anisotropy, Schottky anomalies in the specific heat and suppression of the superconducting transition temperature due to magnetic impurities. In agreement with previous discussions crystal field effects are found to clarify the systematics of magnetic transition temperature, but not to give a full explanation. Other phenomena, such as discrepancies in the magnetic moment of ErRh₄B₄ as measured by neutron diffraction and by Mo¨ssbauer spectroscopy cannot be explained as crystal field related phenomena.     

Manifestation of intramolecular hydrogen bonds in the IR spectra of bioactive aminophenols

The intermolecular interactions in solutions of aminophenols in CCl₄ are studied by the methods of IR Fourier spectroscopy. If the hydroxyl groups of aminophenol molecules occupy the ortho positions with respect to the amino groups of the molecules, the hydroxyl and amino groups are involved in intramolecular interactions with the formation of hydrogen bonds O-H...N and N-H...O. The introduction of two additional tert-butyl groups into the structure of the aminophenol molecule facilitates the formation of O-H...N bonds and impedes the formation of N-H...O bonds. The occurrence of the carbonyl group in the structure of aminophenols leads to the formation of intramolecular hydrogen bonds O-H...O=C. The introduction of the methyl groups into carbonyl-containing aminophenols transforms the O-H...O=C bond into the hydrogen bond N-H...O=C.     

Temperature variation of the Debye-Waller factors of Ba++ and F− ions in BaF2 powder by x-ray diffraction

The temperature variation of the Debye-Waller factors of Ba⁺⁺ and F⁻ ions in BaF₂ powder has been studied using x-ray powder diffraction over the temperature range 77°–298°K. A continuous flow cryostat has been specially fabricated for this purpose for the YPC 50 NM powder diffractometer available in the department. The Debye-Waller factors of Ba⁺⁺ and F⁻ between room temperature and 879°K have been measured using single crystal neutron diffraction by Cooperet al. Theoretical lattice dynamics shell model calculations using a 7-parameter model in a quasiharmonic approximation have been done over a temperature range 77° to 879°K. The theoretical values have been compared with the present x-ray measurements and the single crystal neutron diffraction values and the results are discussed.     

Vibrational spectra and structural studies of nonlinear optical crystal ammonium D,L‐tartrate: a density functional theoretical approach

Single crystals of ammonium D , L ‐tartrate, a potential nonlinear optical (NLO) material of interest, were grown by the slow evaporation technique. The crystal structure was determined by single‐crystal X‐ray diffraction. Fourier transform infrared and Raman spectra of the crystallized molecule were recorded and analyzed. The geometry, intermolecular hydrogen bonding, first hyperpolarizability and harmonic vibrational wavenumbers were calculated with the help of B3LYP density functional theory method. The red shift of hydroxyl and NH₄⁺ stretching wavenumbers indicate the formation of inter‐ and intramolecular hydrogen bonding. Simultaneous activation of CH stretching wavenumbers shows the presence of intramolecular charge transfer in the molecule. Natural bond orbital analysis was carried out to demonstrate the various inter‐ and intramolecular interactions that are responsible for the stabilization of this molecule, leading to high NLO activity. Copyright © 2010 John Wiley & Sons, Ltd.     

The Goldanskii-Karyagin effect in α-SnF2: A comparison of Mössbauer and neutron diffraction results

A single crystal of α-SnF₂ has been subjected to analysis by neutron diffraction at four different temperatures in order to evaluate the Goldanskii-Karyagin effect. The values of the anisotropy parameter, g₁₁, obtained from the neutron diffraction data are lower than those obtained by Mössbauer spectroscopy.     

Quantum Differences between Heavy and Light Water

The structures of heavy and light water at ambient conditions are investigated with the combined techniques of x-ray diffraction, neutron diffraction, and computer simulation. It is found that heavy water is a more structured liquid than light water. We find the OH bond length in H2O is approximately 3% longer than the OD bond length in D2O. This is a much larger change than current predictions. Corresponding to this, the hydrogen bond in light water is approximately 4% shorter than in heavy water, while the intermolecular HH distance is approximately 2% longer.     

Crystal and Magnetic Structures of Granular Powder Spinel Mn–Zn and Ni–Zn Ferrites

Some specific features of the crystal and magnetic structures of granular powder spinel-like ferrites Mn_0.160Mg_0.404Zn_0.448Fe₂O₄, Mn_0.676Zn_0.227Fe_0.09Fe₂O₄, Mn_0.5792Zn_0.2597Fe_0.1612Fe₂O₄, and Ni_0.32Zn_0.68Fe₂O₄ have been studied by neutron diffraction. It has been established that the crystal structure of all the studied compounds has a cubic symmetry with space group Fd\(\bar 3\)m. Ferrimagnetic ordering is observed in all the studied structures. Based on the experimental data, the unit cell parameters and interatomic bond lengths of the studied compounds are determined alongside with the distribution of cations between octahedral and tetrahedral crystallographic positions in their cubic crystal structure. Corresponding average magnetic moments are calculated for different positions in their cubic structure. Some structural mechanisms of the formation of magnetic properties depending on the level of doping and the size of powder grains are discussed.     

Structural aspects of the antiferroelectric-paraelectric phase transition in double perovskite Pb2MgWO6 at high pressures and temperatures

The crystal structure of antiferroelectric Pb₂MgWO₆ has been studied using neutron diffraction at high pressures to 5.4 GPa at room temperature and energy-dispersive X-ray diffraction at high pressures to 4 GPa in the temperature range 300–400 K. At normal conditions, in Pb₂MgWO₆, there is an antiferroelectric phase with the crystal structure described by the orthorhombic symmetry with space group Pnma. At temperature T = 313 K and normal pressure or at room temperature and pressure P ～ 0.9 GPa, the crystal under-goes a structural phase transition to the cubic phase with space group $Fm\bar 3m$ (paraelectric phase). The temperature and pressure dependences of the lattice parameters, unit cell volume, and interatomic bond lengths have been obtained, and the thermal expansion coefficients and the bulk moduli have been calculated for the antiferroelectric and paraelectric phases of Pb₂MgWO₆.     

The two-dimensional neutron diffraction study of the crystal structure of deuterated 4-nitroaniline C6H2D2NO2ND2

Neutron diffraction on a single crystal of partly deuterated 4-nitroaniline C₆H₂D₂NO₂ND₂ yielded the integrated intensities of 145 independenth0l reflections. The positional and thermal vibration parameters were refined by the least squares procedure, a finalR-index of 0·135 was achieved. TheX andZ fractional coordinates of the carbon atoms of the benzene ring and the nitrogen atoms were found to be the same as those in Trueblood's three-dimensional X-ray analysis, but the coordinates of outer oxygen and hydrogen atoms were shifted. The positions of two oxygen atoms in the nitrogroup and two deuterium atoms in the aminogroup indicate the shorter hydrogen bridges between neighbouring molecules. The bonds between two hydrogen and two deuterium atoms and corresponding carbon atoms of the benzene ring appeared to be longer than the bonds resulting from X-ray data.The authors thank Dr. J. Honzl and M. Metalová for kindly supplying the deuterated 4-nitroaniline, Dr. M. ivanovi for facilitating the neutron diffraction measurements and Dr. K. Toman and Dr. B. Sedláek for enabling the computer treatment of the data.