The ordered phase of methylammonium lead chloride CH3ND3PbCl3

The perovskite-structured compound methylammonium lead chloride orders into a low-temperature phase of space group Pnma, in which at 80 K each of the orthorhombic axes , and is doubled with respect to the room temperature disordered cubic phase (). The structure was solved by ab initio methods using the programs EXPO and FOX. This unusual cell basis for space group Pnma is not that of a standard tilt system. This phase, in which the methylammonium ions, are ordered shows distorted octahedra. The octahedra possess a bond angle variance of 60.663°² and a quadratic elongation of 1.018, and are more distorted than those in the ordered phase of methylammonium lead bromide. There is also an alternating long and short Pb-Cl bond along a, due to an off-center displacement of Pb within the octahedron. This suggests that the most rigid unit is actually the methylammonium cation, rather than the PbCl₆ octahedra, in agreement with existing spectroscopic data.     

Structure and dynamics of ND3BF3 in the solid and gas phases: a combined NMR,neutron diffraction,and Ab initio study

The decrease in D-->A bond lengths, previously reported for some Lewis acid/base complexes, in going from the gas to the solid phases is investigated by obtaining an accurate crystal structure of solid ND(3)BF(3) by powder neutron diffraction. The B-N internuclear distance is 1.554(3) A, 0.118 A shorter than the most recent gas-phase microwave value and 0.121 A shorter than the single molecule geometry optimized (1.672 A, CISD/6-311++G(d,p)) bond length. The crystal structure also shows N-D.F-B hydrogen bonds. The effects of this change in structure and of intermolecular hydrogen-bonding on nuclear magnetic shielding (i.e., chemical shifts) and the nuclear quadrupolar coupling constants (QCC) are investigated by ab initio molecular orbital and density functional theory calculations. These calculations show that the nitrogen ((15)N and (14)N) and boron ((11)B and (10)B) chemical shifts should be rather insensitive to changes in r(BN) and that the concomitant changes in molecular structure. Calculations on hydrogen-bonded clusters, based on the crystal structure, indicate that H-bonding should also have very little effect on the chemical shifts. On the other hand, the (11)B and (14)N QCCs show large changes because of both effects. An analysis of the (10)B[(19)F] line shape in solid ND(3)(10)BF(3) yields a (11)B QCC of +/-0.130 MHz. This is reasonably close an earlier value of +/-0.080 MHz and the value of +/-0.050 MHz calculated for a [NH(3)BF(3)](4) cluster. The gas-phase value is 1.20 MHz. Temperature-dependent deuterium T(1) measurements yield an activation energy for rotation of the ND(3) group in solid ND(3)BF(3) of 9.5 +/- 0.1 kJ/mol. Simulations of the temperature-dependent T(1) anisotropy gave an E(a) of 9.5 +/- 0.2 kJ/mol and a preexponential factor, A, of 3.0 +/- 0.1 x 10(12) s(-)(1). Our calculated value for a [NH(3)BF(3)](4) cluster is 16.4 kJ/mol. Both are much higher than the previous value of 3.9 kJ/mol, from solid-state proton T(1) measurements.     

Ammonium cyanate shows N-H...N hydrogen bonding, not N-H...O

The transformation of ammonium cyanate into urea, first studied over 170 years ago by W?hler and Liebig, has an important place in the history of chemistry. To understand the nature of this solid state reaction, knowledge of the crystal structure of ammonium cyanate is a prerequisite. Employing neutron powder diffraction, we demonstrate conclusively that, in the structure of ammonium cyanate, the NH(4)(+) cation forms N-H...N hydrogen bonds to four cyanate N atoms at alternate corners of a distorted cube, rather than our previously proposed alternative arrangement with N-H...O hydrogen bonds to cyanate O atoms at the other four corners.     

Novel coexistence of superconductivity with two distinct magnetic orders

The heavy fermion system exhibits properties that range from an incommensurate antiferromagnet for small to an exotic superconductor on the Ir-rich end of the phase diagram. At intermediate where antiferromagnetism coexists with superconductivity, two types of magnetic order are observed: the incommensurate one of and a new, commensurate antiferromagnetism that orders separately. The coexistence of -electron superconductivity with two distinct -electron magnetic orders is unique among unconventional superconductors, adding a new variety to the usual coexistence found in magnetic superconductors.     

Investigating the mechanisms of diamond polishing using Raman spectroscopy

Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe₃O₄) and haematite (α-Fe₂O₃), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides.     

Origin of low-frequency local vibrational modes in high density amorphous ice

Incoherent-inelastic neutron scattering data are obtained from 5-80 K for high-density amorphous (hda) ice in the region 0-135 cm(-1). An excess contribution to the vibrational density of states is identified near 20 cm(-1). The origin of these vibrations has been identified by lattice dynamics calculations on an "experimental" structure derived from reverse Monte Carlo analysis of hda ice neutron diffraction data. An interpretation that localized oscillations of short chains and isolated water molecules are responsible for the excess low-frequency modes is consistent with our data.     

Testing heteroscedasticity by wavelets in a nonparametric regression model

In the nonparametric regression models, a homoscedastic structure is usually assumed. However, the homoscedasticity cannot be guaranteed a priori. Hence, testing the heteroscedasticity is needed. In this paper we propose a consistent nonparametric test for heteroscedasticity, based on wavelets. The empirical wavelet coefficients of the conditional variance in a regression model are defined first. Then they are shown to be asymptotically normal, based on which a test statistic for the heteroscedasticity is constructed by using Fan's wavelet thresholding idea. Simulations show that our test is superior to the traditional nonparametric test.     

Testing coeffcients of AR and bilinear time series models by a graphical approach

AR and bilinear time series models are expressed as time series chain graphical models, based on which, it is shown that the coefficients of AR and bilinear models are the conditional correlation coefficients conditioned on the other components of the time series. Then a graphically based procedure is proposed to test the significance of the coeffcients of AR and bilinear time series. Simulations show that our procedure performs well both in sizes and powers.