RESUMO
The experimental neutron and x-ray diffraction data for stoichiometric and S-deficient Ge(x)As(x)S(100-2x) glasses with x = 18.2, 25.0, and 33.3 at.% have been modeled simultaneously using the reverse Monte Carlo (RMC) technique. Nearest-neighbor coordination environments, as obtained in previous x-ray absorption spectroscopy and diffraction experiments, have been employed as short-range order constraints in these simulations. The large scale three-dimensional structural models thus obtained from RMC simulation are used to investigate the nature and compositional evolution of intermediate-range structural order in these ternary glasses. The intermediate-range structural order is controlled by (1) a corner-shared three-dimensional network of AsS(3) pyramids and GeS(4) tetrahedra in the stoichiometric Ge(18.2)As(18.2)S(63.6) glass, (2) a heterogeneous structure that consists of homopolar bonded As-rich regions coexisting with a GeS(2) network in the S-deficient Ge(25)As(25)S(50) glass, and (3) a homogeneous structure resulting from the disruption of the topological continuity of the GeS(2) network and As-rich clusters regions due to the formation of Ge-As bonds in the most S-deficient Ge(33.3)As(33.3)S(33.3) glass. This scenario of the compositional evolution of intermediate-range structural order is consistent with and provides an atomistic explanation of the corresponding evolution in the position, width and intensity of the first sharp diffraction peak and the magnitude of small angle scattering in these glasses.
RESUMO
In the communication by Kurita et al 2007 J. Phys.: Condens. Matter 19 152101, peaks in the liquid diffraction pattern of triphenyl phosphite have been attributed to intermolecular phosphor-phosphor distances. Based on our previous neutron and x-ray diffraction studies we argue that this assignment is incorrect and the peak contributions are likely to be much more complex.
RESUMO
Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structure of the glacial and supercooled liquid states in triphenyl phosphite. The observed diffraction patterns have been interpreted using a Reverse Monte Carlo modeling technique. The results show that the glacial state forms unusually weak intermolecular hydrogen bonds between an oxygen atom connected to a phenyl ring and an adjacent phenyl ring aligned in an approximately antiparallel configuration. The structure is very different from the hexagonal crystal which is characterized by two weaker hydrogen bonds between linear arrays of molecules which are offset from each other and packed in a hexamer arrangement.
RESUMO
The structure of liquid deuterium fluoride has been measured using pulsed neutron diffraction and high energy x-ray diffraction techniques as a function of temperature. The neutron experiments were performed at T=296+/-2 K, 246+/-2 K, and 193+/-2 K and the x-ray measurements carried out at 296+/-2 K and 195+/-2 K. The x-ray pair correlation functions, which are dominated by fluorine-fluorine interactions, show the first peak at approximately 2.53+/-0.05 A remains very nearly invariant with decreasing temperature. Peaks around 4.5 and 5.0 A also appear at both temperatures in the x-ray data. In contrast, the intermolecular peaks in the total neutron pair correlation function show that significant systematic local structural changes occur as the temperature is lowered. The first intermolecular peak position shortens from 1.64+/-0.05 A at 296 K to 1.56+/-0.05 A at 195 K. Although there are overlapping contributions from the intermolecular hydrogen-fluorine and hydrogen-hydrogen correlations, it is clear that the temperature dependent structural changes are largely due to a rearrangement of the deuterium atom positions in the fluid. By comparison with partial structure factor data the hydrogen bonds appear to become more linear at lower temperatures.
