Knowledge of atomic diffusion is a fundamental issue in synthesis and stability of materials. Direct studies of the elementary diffusion event, that is, how the individual atoms 'jump', are scarce, as the available techniques are limited to selected systems. Here we show how by monitoring the spatial and temporal variations of the scattered coherent X-ray intensity the diffusion of single atoms can be studied. This is demonstrated for the intermetallic alloy Cu(90)Au(10). By measuring along several directions in reciprocal space, we can elucidate the dynamical behaviour of single atoms as a function of their neighbourhood. This method, usually referred to as X-ray photon correlation spectroscopy (XPCS), does not rely on specific atomic species or isotopes and can thus be applied to almost any system. Thus, given the advent of the next-generation X-ray sources, XPCS has the potential to become the main method for quantitatively understanding diffusion on the atomic scale.

The Mössbauer effect of 57Fe-enriched samples was used to investigate the coupling of 80% sucrose/water, a protein-stabilizing solvent, to vibrational and diffusive modes of the heme iron of CO-myoglobin. For comparison we also determined the Mössbauer spectra of K4 57Fe (CN)6 (potassium ferrocyanide, PFC), where the iron is fully exposed in the same solvent. The temperature dependence of the Mössbauer parameters derived for the two samples proved to be remarkably similar, indicative of a strong coupling of the main heme displacements to the viscoelastic relaxation of the solvent. We show that CO escape out of the heme pocket couples to the same type of fluctuations, whereas intramolecular bond formation involves solvent-decoupled heme deformation modes that are less prominent in the Mössbauer spectrum. With respect to other solvents, however, sucrose shows a reduced viscosity effect on heme displacements and the kinetics of ligand binding due to preferential hydration of the protein. This result confirms thermodynamic predictions of the stabilizing action of sucrose by a dynamic method.

The confinement of materials in low-dimensional structures has significant impact on propagating excitations like phonons. Using the isotope-specific 57Fe nuclear resonant vibrational spectroscopy we were able to determine elastic and thermodynamic properties of ultrathin Fe films on W(110). With decreasing thickness one observes a significant increase of the mean atomic displacement that goes along with an enhancement of vibrational modes at low energies as compared to the bulk. The analysis reveals that these deviations result from atomic vibrations of the single atomic layers at the two boundaries of the film, while the atoms inside the films vibrate almost bulklike.

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Abslrad. The phonon dispersion of iron-rich FBSi alloys of DO3 struclwe (space gmup F m -3m) has been studied by inelastic neulron scaltering. The mea~wements were carried out on two crystals of different composition: Fe7,Siz at 20 and 930°C. and FesoSilo at 20. 930 and IIOO'C. The respective degree of order was determined by powder diffraction measurements. A general decrease of phonon frequencies with increasing temperature is found. the temperature dependence being strongest for lransvene phonons with IB50] propagation. With decreasing order, phonon gaps close and lhe highest optical band degeuerates into a broad distribution of inelastic intensity due to disorder scattering, The dependence of the dispersion on lhe alloy composition is nM very pronounced. The migration enthalpies as well as several other thermodynamic quantities have been calculated from the densities of states. Although the low frequencies of the uansverae phonons indicate particularly Imv migsation barriers. they o ~o t explain the pronounced change of the diffusivity with composition. This composition dependence is tentatively explained by high vacancy concenmtions.

We observed that diffuse interfaces sharpen rather than broaden in completely miscible ideal binary systems. This is shown in situ during heat treatments at gradually increasing temperatures by scattering of synchrotron radiation in coherent Mo/V multilayers containing initially diffuse interfaces. This effect provides a useful tool for the improvement of interfaces and offers a way to fabricate better x-ray or neutron mirrors, microelectronic devices, or multilayers with giant magnetic resistance.