We have probed both the local structure and the electronic properties of Na-containing type II Si clathrates by x-ray absorption spectroscopy. The near-edge region of the spectrum is particularly sensitive to the local structure surrounding the Na atom. Through experimental investigations of a series of eight samples with general formula Na x Si 136 , with x ranging from ϳ0 to 21.5, and simulation of extended x-ray absorption fine structure ͑EXAFS͒ and x-ray absorption near-edge structure spectra ͑XANES͒, we find that Na is primarily in the larger Si 28 cages at low loadings, and loss of the Na relative to full cage occupancy occurs preferentially from the smaller Si 20 cages. Our EXAFS results also show that Na is dynamically disordered in the Si 28 cages but less disordered at higher Na loadings. Local-orbital density of states calculations indicate that the Na in the Si 20 cage has a charge of 0.7e − while Na in the Si 28 cages has a slightly higher ͑loading-dependent͒ charge ͑0.72e − to 0.8e − ͒.

We describe a laboratory experiment that serves as an introduction to solid-state and materials science, a topic that requires additional attention in the undergraduate chemistry laboratory curriculum. The experiment illustrates the longrange translational order, crystal growth, and the macroscopic manifestations of that order. This is demonstrated through the preparation and characterization of large, well-formed bismuth crystals, an aesthetically pleasing product. The characterization of the grown bismuth crystals involves determination of melting point and enthalpy of fusion via differential scanning calorimetry. The temperature dependence of the electrical resistance of grown bismuth crystals is also measured. Students are encouraged to consider the effect of metallic bonding interactions on the melting of the crystal samples and on their ability to conduct electricity. Students also analyze how the impurities influence the melting point and the electrical properties. The experiment is suitable for use in the third-or fourth-year undergraduate laboratory and is performed by students in one four-hour session. The experiment could be adapted to two laboratory sessions, with the first two-hour session covering crystal growth, and the second two-hour session focused on thermal and electrical characterization.

Thermal properties of a series of type II clathrates of the formula NaxSi136 with 0 < x < 24 and Na guests occupying the Si cages have been investigated over the temperature range from 2 to 300 K. Heat capacity and thermal conductivity results show that the structure is remarkably responsive to the loading of Na guests. The response is phononic: the host lattice expands in a non-monotonic way, and first stiffens, then relaxes at low loading into the larger Si28 cages (x < 9), then stiffens again as the Na concentration increases further. The response is also electronic, through changes in electronic properties as additional Na is loaded into the smaller Si20 cages at high loading (x > 9). In total, the influence of the guest loading illustrates the complexities of structure-property relations in a guest-host system.

Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3-100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed silicon nanocrystals that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.

The Nitrogen 1s near edge X-ray absorption fine structure (NEXAFS) of gallium nitride (GaN) shows a strong natural linear dichroism that arises from its anisotropic wurtzite structure. An additional spectroscopic variation arises from lattice strain in epitaxially grown GaN thin films. This variation is directly proportional to the degree of strain for some spectroscopic features. This strain variation is interpreted with the aid of density functional theory calculations.