Hydrogen-bonded assembly of methanol on Cu(111)

Investigation of methanol's surface chemistry on metals is a crucial step towards understanding the reactivity of this important chemical feedstock. Cu is a relevant metal for methanol synthesis and reforming, but due to the weak interaction of methanol with Cu, an atomic scale view of methanol's coverage-dependent ordering and self-assembly on Cu(111), the most abundant facet of most nanoparticles, has not yet been possible. Low and variable temperature scanning tunneling microscopy coupled with density functional theory reveal a coverage-dependent range of highly ordered structures stabilized by two hydrogen bonds per molecule. While extended chains that resemble the hydrogen-bonded zigzag structures reported for solid methanol are an efficient way to pack methanol at higher coverages, lower surface coverages yield isolated hexamer units. These hexamers form the same number of hydrogen bonds as the chains but appear to repel one another on the surface. Annealing treatments lead to the desorption of methanol with almost no decomposition. This data serves as a useful guide to both the preferred adsorption geometries and energies of a variety of methanol structures on Cu(111) surfaces as a function of surface coverage.     

Revisiting the structure of the p(4 x 4) surface oxide on Ag(111)

Scanning tunneling microscopy (STM) and density-functional theory are used to reexamine the structure of the renowned p(4 x 4)-O/Ag(111) surface oxide. The accepted structural model [C. I. Carlisle, Phys. Rev. Lett. 84, 3899 (2000)10.1103/PhysRevLett.84.3899] is incompatible with the enhanced resolution of the current STM measurements. An "Ag6 model" is proposed that is more stable than its predecessor and accounts for the coexistence of the p(4 x 4) and a novel c(3 x 5log3)rect phase. This coexistence is an indication of the dynamic complexity of the system that until now has not been appreciated.     

Manipulation and control of hydrogen bond dynamics in absorbed ice nanoclusters

Inelastic electron tunneling is used to explore the dynamics of ice nanoclusters adsorbed on Ag(111). The diffusion of entire nanoclusters or internal hydrogen bond rearrangement can be selectively controlled by injecting electrons either directly into the clusters themselves or indirectly ("indirect inelastic electron tunneling") into the substrate at distances of up to 20 nm from them; a reaction probability that oscillates with the tip-cluster lateral distance presents evidence that surface state electrons mediate the excitation. Density functional theory calculations reveal a strong sensitivity of the computed activation energies of the individual processes to the applied electrical field.     

Assembly of a photoreactive coordination polymer containing rectangular grids

We describe the synthesis, crystal structure and solid state reactivity of cadmium fumarate dihydrate, which is made up of planar H-bonded metal-organic layers and undergoes, upon irradiation, a topochemical [2 + 2] cycloaddition reaction.     

Thermal emission of pions in antiproton-proton annihilation at 12 GeV/c

Using data of \(\bar pp\) annihilation at 12 GeV/c we have found that centrally-emitted pions follow a thermal energy spectrum with an inclusive temperature of 111±2 MeV, the same as has been found for pions produced in πp collisions at 16 GeV/c. An analysis of individual high-multiplicity events to search for fluctuations in the temperature parameter on an event-byevent basis has been made, using two different methods. We obtained the value 0.18±0.02 for the relative dispersion of the temperature fluctuations.     

Globally flexible functional forms: The neural distance function

The output distance function is a key concept in economics. However, its empirical estimation often violates properties dictated by neoclassical production theory. In this paper, we introduce the neural distance function (NDF) which constitutes a global approximation to any arbitrary production technology with multiple outputs given by a neural network (NN) specification. The NDF imposes all theoretical properties such as monotonicity, curvature and homogeneity, for all economically admissible values of outputs and inputs. Fitted to a large data set for all US commercial banks (1989–2000), the NDF explains a very high proportion of the variance of output while keeping the number of parameters to a minimum and satisfying the relevant theoretical properties. All measures such as total factor productivity (TFP) and technical efficiency (TE) are computed routinely. Next, the NDF is compared with the Translog popular specification and is found to provide very satisfactory results as it possesses the properties thought as desirable in neoclassical production theory in a way not matched by its competing specification.     

Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics

The impact of quantum nuclear effects on hydrogen (H-) bond strength has been inferred in earlier work from bond lengths obtained from path integral molecular dynamics (PIMD) simulations. To obtain a direct quantitative assessment of such effects, we use constrained-centroid PIMD simulations to calculate the free energy changes upon breaking the H-bonds in dimers of HF and water. Comparing ab initio simulations performed using PIMD and classical nucleus molecular dynamics (MD), we find smaller dissociation free energies with the PIMD method. Specifically, at 50 K, the H-bond in (HF)(2) is about 30% weaker when quantum nuclear effects are included, while that in (H(2)O)(2) is about 15% weaker. In a complementary set of simulations, we compare unconstrained PIMD and classical nucleus MD simulations to assess the influence of quantum nuclei on the structures of these systems. We find increased heavy atom distances, indicating weakening of the H-bond consistent with that observed by direct calculation of the free energies of dissociation.