A Most Enantioselective Chiral Surface: Tartaric Acid on All Surfaces Vicinal to Cu(110).

Enantioselective chemistry on intrinsically chiral surfaces is the quintessential form of structure-sensitive surface chemistry, arising purely from the dissymmetry of the surface structure. Identification or design of chiral surface structures that maximize enantioselectivity for a given processes is extremely challenging because of the limited magnitude of the enantiospecific interaction energetics of chiral molecules with chiral surfaces. Using spherical Cu single crystals exposing surfaces with a continuous two-dimensional distribution of crystallographic orientations, we mapped the enantiospecific surface reaction kinetics of tartaric acid decomposition across the surface orientation space. These measurements reveal both the mechanistic origin of enantioselectivity and identify the structural features of the most enantiospecific surface orientation.

Detection of CuAuPd Phase Boundaries Using Core Level Shifts.

A high throughput study has been conducted of the Cu 2p3/2, Au 4f7/2, and Pd 3d3/2 X-ray photoemission spectra obtained from a continuous distribution of CuxAuyPd1-x-y alloy samples prepared as a single composition spread alloy film (CSAF). All three elements exhibit shifts of their core level binding energies with respect to their pure states when diluted into the alloy. The Cu 2p3/2 core level shift (CLS) exhibits additional shifts over the composition ranges at which the CuxAuyPd1-x-y alloy transitions between FCC and B2 phases. This discontinuous CLS has been used to map the extent of the B2 phase across the ternary CuxAuyPd1-x-y alloy composition space. The sensitivity of core level binding energies to the alloy phase offers an opportunity to use XPS to study phases in alloy nanoparticles, ultrathin films, and other morphologies that are not amenable to structure determination by diffraction based methods.

Observation of a one-dimensional adsorption site on carbon nanotubes: adsorption of alkanes of different molecular lengths.

Three well-defined adsorption sites have been found on opened single-wall carbon nanotubes by temperature-programmed desorption measurements for several alkanes. A series of linear chain alkanes from pentane to nonane, as well as a branched alkane molecule, 2,2,4-trimethylpentane, were used to elucidate the effect of molecular length on the capacity of the adsorption sites. The two highest-energy adsorption sites were assigned as the nanotube interior sites and groove sites on the outside of the nanotube bundles. Hybrid Monte Carlo simulations were performed to probe the molecular-level details of adsorption. Both in experiments and in the simulation, the groove sites were seen to behave as one-dimensional adsorption space, demonstrating an inverse dependence of capacity on the length of the adsorbed molecule. In contrast, the capacity of the internal sites was found to depend inversely on the volume occupied by the molecule.

Analytical formulas for Fermi resonance interactions in continuous distributions of states.

Fermi resonance interaction between a distributed fundamental vibrational level and a distributed overtone is considered. The overtone is assumed to be spectrally inactive. Simple analytical expressions are derived for the resulting spectral profile in terms of the distribution functions for the fundamental and overtone. The formulas enable straightforward modeling of spectra with Fermi resonances.

Molecular views of physical adsorption inside and outside of single-wall carbon nanotubes.

We discuss our own studies of molecular adsorption on and inside of single-wall carbon nanotubes in the broader context of important theoretical and experimental developments in the field. We show that adsorption in the nanotube interior sites as well as in the groove and exterior sites may be resolved by various experimental methods. In addition, the changes that the adsorbate phases undergo due to confinement in the nanotube interior are discussed, particularly focusing on confined molecules of water, alkanes, and an alkene. Attention is also devoted to the use of oxidizing agents such as ozone to open the ends and walls of nanotubes for interior adsorption.

Adsorption of CF4 on the internal and external surfaces of opened single-walled carbon nanotubes: a vibrational spectroscopy study.

Infrared spectroscopy has been used to make the first experimental discrimination between molecules bound by physisorption on the exterior surface of carbon single-walled nanotubes (SWNTs) and molecules bound in the interior. In addition, the selective displacement of the internally bound molecules has been observed as a second adsorbate is added. SWNTs were opened by oxidative treatment with O(3) at room temperature, followed by heating in a vacuum to 873 K. It was found that, at 133 K and 0.033 Torr, CF(4) adsorbs on closed SWNTs, exhibiting its nu(3) asymmetric stretching mode at 1267 cm(-1) (red shift relative to the gas phase, 15 cm(-1)). Adsorption on the nanotube exterior is accompanied by adsorption in the interior in the case of opened SWNTs. Internally bound CF(4) exhibits its nu(3) mode at 1247 cm(-1) (red shift relative to the gas phase, 35 cm(-1)). It was shown that, at 133 K, Xe preferentially displaces internally bound CF(4) species, and this counterintuitive observation was confirmed by molecular simulations. The confinement of CF(4) inside (10,10) single-walled carbon nanotubes does not result in the production of lattice modes that are observed in large 3D ensembles of CF(4).