The techniques of neutron diffraction and x-ray diffraction, as applied to structural studies of liquids and glasses, are reviewed. Emphasis is placed on the explanation and discussion of the experimental techniques and data analysis methods, as illustrated by the results of representative experiments. The disordered, isotropic nature of the structure of liquids and glasses leads to special considerations and certain difficulties when neutron and x-ray diffraction techniques are applied, especially when used in combination on the same system. Recent progress in experimental technique, as well as in data analysis and computer simulation, has motivated the writing of this review.

We determined the structure of the hydrated Cu(II) complex by both neutron diffraction and first-principles molecular dynamics. In contrast with the generally accepted picture, which assumes an octahedrally solvated Cu(II) ion, our experimental and theoretical results favor fivefold coordination. The simulation reveals that the solvated complex undergoes frequent transformations between square pyramidal and trigonal bipyramidal configurations. We argue that this picture is also consistent with experimental data obtained previously by visible near-infrared absorption, x-ray absorption near-edge structure, and nuclear magnetic resonance methods. The preference of the Cu(II) ion for fivefold instead of sixfold coordination, which occurs for other cations of comparable charge and size, results from a Jahn-Teller destabilization of the octahedral complex.

The full set of partial structure factors for the prototypical network glass GeSe2 was measured using the method of isotopic substitution in neutron diffraction. The basic building block of the network is the Ge(Se(1/2))(4) tetrahedron in which 34(5)% of the Ge reside in edge-sharing configurations. The intrinsic chemical order of the glass is, however, broken with a maximum of 25(5)% Ge and 20(5)% Se being involved in homopolar bonds at distances of 2.42(2) and 2.32(2) A, respectively.

Atomic ordering in network glasses on length scales longer than nearest-neighbour length scales has long been a source of controversy. Detailed experimental information is therefore necessary to understand both the network properties and the fundamentals of glass formation. Here we address the problem by investigating topological and chemical ordering in structurally disordered AX2 systems by applying the method of isotopic substitution in neutron diffraction to glassy ZnCl2. This system may be regarded as a prototypical ionic network forming glass, provided that ion polarization effects are taken into account, and has thus been the focus of much attention. By experiment, we show that both the topological and chemical ordering are described by two length scales at distances greater than nearest-neighbour length scales. One of these is associated with the intermediate range, as manifested by the appearance in the measured diffraction patterns of a first sharp diffraction peak at 1.09(3) A(-1); the other is associated with an extended range, which shows ordering in the glass out to 62(4) A. We also find that these general features are characteristic of glassy GeSe2, a prototypical covalently bonded network material. The results therefore offer structural insight into those length scales that determine many important aspects of supercooled liquid and glass phenomenology.

The partial structure factors of bulk-quenched glassy GeSe2 were measured by using the method of isotopic substitution in neutron diffraction to enable the first detailed comparison at the partial pair distribution function level of a covalently bonded network system in both its glassy and liquid phases. The results show that the basic building block of the glass is the Ge(Se1/2)4 tetrahedron in which 34(5)% of the Ge atoms reside in edge-sharing configurations. The intrinsic chemical order of the glass is, however, broken with a maximum of 25(5)% Ge and 20(5)% Se being involved in homopolar bonds at distances of 2.42(2) and 2.32(2) Å, respectively, which is consistent with the existence of these features in the liquid phase of GeSe2. Like for the liquid, concentration fluctuations in the glass are found to extend over distances characteristic of the intermediate-range atomic ordering as manifested by the appearance of a first sharp diffraction peak at 1.00(2) Å−1 in the Bhatia–Thornton concentration–concentration partial structure factor. A comparison is made between the measured partial structure factors and recent first principles molecular dynamics simulations for the glassy and liquid phases. It is found that the most significant disagreement between experiment and simulation occurs with respect to the Ge–Ge correlations and that the simulated results for the glass are too liquid-like, reflecting the use of a quench time greatly in excess of that achieved experimentally.

27The structure of liquid alumina at a temperature ≈2400 K near to its melting point was measured using 28 neutron and high-energy x-ray diffraction by employing containerless aerodynamic-levitation and laser-29 heating techniques. The measured diffraction patterns were compared to those calculated from molecular 30 dynamics simulations using a variety of pair potentials, and the model found to be in best agreement with 31 experiment was refined by using the reverse Monte Carlo (

The full set of partial structure factors for glassy germania, or GeO, were accurately measured by using the method of isotopic substitution in neutron diffraction in order to elucidate the nature of the pair correlations for this archetypal strong glass former. The results show that the basic tetrahedral Ge(O) building blocks share corners with a mean inter-tetrahedral Ge-Ô-Ge bond angle of 132(2)°. The topological and chemical ordering in the resultant network displays two characteristic length scales at distances greater than the nearest neighbour. One of these describes the intermediate range order, and manifests itself by the appearance of a first sharp diffraction peak in the measured diffraction patterns at a scattering vector k≈1.53 Å, while the other describes so-called extended range order, and is associated with the principal peak at k = 2.66(1) Å. We find that there is an interplay between the relative importance of the ordering on these length scales for tetrahedral network forming glasses that is dominated by the extended range ordering with increasing glass fragility. The measured partial structure factors for glassy GeO are used to reproduce the total structure factor measured by using high energy x-ray diffraction and the experimental results are also compared to those obtained by using classical and first principles molecular dynamics simulations.

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