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C J Benmore

Publications and source records attributed to C J Benmore.

9 recordsLinked to original sources
PubMed2006

Adding a length scale to the polyamorphic ice debate.

X-ray scattering and molecular dynamics simulations have been used to correlate the short range oxygen-oxygen structure with the intermediate range ordering (IRO) upon annealing very high density amorphous ice. While it is clear that the IRO that defines the network structure breaks down continuously to a minimum level, where there are weakened correlations extending beyond 7 Angstrom, at this point the local structure (O-O-O angles) is observed to change abruptly, allowing a continuous reemergence of a new IRO network. This is very different from a classic first order transition and helps reconcile previous data.

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PubMed2006

Orientational correlations in the glacial state of triphenyl phosphite.

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.

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PubMed2006

Isotope quantum effects in water around the freezing point.

We have measured the difference in electronic structure factors between liquid H(2)O and D(2)O at temperatures of 268 and 273 K with high energy x-ray diffraction. These are compared to our previously published data measured from 279 to 318 K. We find that the total structural isotope effect increases by a factor of 3.5 over the entire range, as the temperature is decreased. Structural isochoric temperature differential and isothermal density differential functions have been used to compare these data to a thermodynamic model based upon a simple offset in the state function. The model works well in describing the magnitude of the structural differences above approximately 310 K, but fails at lower temperatures. The experimental results are discussed in light of several quantum molecular dynamics simulations and are in good qualitative agreement with recent temperature dependent, rotationally quantized rigid molecule simulations.

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PubMed2005

Temperature dependence of isotopic quantum effects in water.

The technique of high energy x-ray diffraction has been used to measure the temperature variation of hydrogen versus deuterium isotopic quantum effects on the structure of water. The magnitude of the effect is found to be inversely proportional to the temperature, varying by a factor of 2.5 over the range 6 to 45 degrees C. In addition, the H216O versus H218O effect has been measured at 26 degrees C and the structural difference shown to be restricted to the nearest neighbor molecular interactions. The results are compared to recent simulations and previously measured isochoric temperature differentials; additionally, implications for H/D substitution experiments are considered.

Computer Simulation↗
PubMed2004

On the variation of the structure of liquid deuterium fluoride with temperature.

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.

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PubMed2004

Formation and structure of a dense octahedral glass.

We have performed in situ x-ray and neutron-diffraction measurements, and molecular dynamics simulations, of GeO2, an archetypal network-forming glass under pressure. Below 5 GPa, additional atoms encroaching on the first tetrahedral shell are seen to be a precursor of local coordination change. Between 6 and 10 GPa, we observe structures with a constant average coordination of approximately 5, indicating a new metastable, intermediate form of the glass. At 15 GPa, the structure of a fully octahedral glass has been measured. This structure is not retained upon decompression and, therefore, must be studied in situ.

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PubMed2003

Intermediate-range order in permanently densified GeO2 glass.

Information about the partial structure factors of densified GeO2 glass has been obtained from neutron and x-ray diffraction measurements. Densification causes a reduction in the length scale of the intermediate range order (IRO). The difference structure factors obtained by combining the x-ray and neutron data so as to eliminate one partial structure factor at a time shows the greatest effects when the Ge-Ge correlations are eliminated and least when O-O correlations are eliminated. This implies that the reduced length scale results from a decrease in the next-nearest neighbor Ge-O and O-O distance caused by a rotation about the Ge-O-Ge bonds and a distortion of the GeO4 tetrahedra.

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PubMed2002

Structural studies of several distinct metastable forms of amorphous ice.

Structural changes during annealing of high-density amorphous ice were studied with both neutron and x-ray diffraction. The first diffraction peak was followed from the high- to the low-density amorphous form. Changes were observed to occur through a series of intermediate forms that appear to be metastable at each anneal temperature. Five distinct amorphous forms were studied with neutron scattering, and many more forms may be possible. Radial distribution functions indicate that the structure evolves systematically between 4 and 8 angstroms. The phase transformations in low-temperature liquid water may be much more complex than currently understood.

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