Delia Fernández-Torre

Point defects on graphene on metals.

Understanding the coupling of graphene with its local environment is critical to be able to integrate it in tomorrows electronic devices. Here we show how the presence of a metallic substrate affects the properties of an atomically tailored graphene layer. We have deliberately introduced single carbon vacancies on a graphene monolayer grown on a Pt(111) surface and investigated its impact in the electronic, structural, and magnetic properties of the graphene layer. Our low temperature scanning tunneling microscopy studies, complemented by density functional theory, show the existence of a broad electronic resonance above the Fermi energy associated with the vacancies. Vacancy sites become reactive leading to an increase of the coupling between the graphene layer and the metal substrate at these points; this gives rise to a rapid decay of the localized state and the quenching of the magnetic moment associated with carbon vacancies in freestanding graphene layers.

Hydrogen activation, diffusion, and clustering on CeO2(111): A DFT+U study

We present a comprehensive density functional theory+U study of the mechanisms underlying the dissociation of molecular hydrogen, and diffusion and clustering of the resulting atomic species on the CeO2(111) surface. Contrary to a widely held view based solely on a previous theoretical prediction, our results show conclusively that H2 dissociation is an activated process with a large energy barrier ~1.0 eV that is not significantly affected by coverage or the presence of surface oxygen vacancies. The reaction proceeds through a local energy minimum--where the molecule is located close to one of the surface oxygen atoms and the H-H bond has been substantially weaken by the interaction with the substrate--, and a transition state where one H atom is attached to a surface O atom and the other H atom sits on-top of a Ce(4+) ion. In addition, we have explored how several factors, including H coverage, the location of Ce(3+) ions as well as the U value, may affect the chemisorption energy and the relative stability of isolated OH groups versus pair and trimer structures. The trimer stability at low H coverages and the larger upward relaxation of the surface O atoms within the OH groups are consistent with the assignment of the frequent experimental observation by non-contact atomic force and scanning tunneling microscopies of bright protrusions on three neighboring surface O atoms to a triple OH group. The diffusion path of isolated H atoms on the surface goes through the adsorption on-top of an oxygen in the third atomic layer with a large energy barrier of ~1.8 eV. Overall, the large energy barriers for both, molecular dissociation and atomic diffusion, are consistent with the high activity and selectivity found recently in the partial hydrogenation of acetylene catalyzed by ceria at high H2/C2H2 ratios.

Graphene Tunable Transparency to Tunneling Electrons: A Direct Tool To Measure the Local Coupling

The local interaction between graphene and a host substrate strongly determines the actual properties of the graphene layer. Here we show that scanning tunneling microscopy (STM) can selectively help to visualize either the graphene layer or the substrate underneath, or even both at the same time, providing a comprehensive picture of this coupling with atomic precision and high energy resolution. We demonstrate this for graphene on Cu(111). Our spectroscopic data show that, in the vicinity of the Fermi level, graphene π bands are well preserved presenting a small n-doping induced by Cu(111) surface state electrons. Such results are corroborated by Angle-Resolved Photoemission Spectra (ARPES) and Density Functional Theory with van der Waals (DFT + vdW) calculations. Graphene tunable transparency also allows the investigation of the interaction between the substrate and foreign species (such as atomic H or C vacancies) on the graphene layer. Our calculations explain graphene tunable transparency in terms of the rather different decay lengths of the graphene Dirac π states and the metal surface state, suggesting that it should apply to a good number of graphene/substrate systems.

WATER-AMMONIUM ICES AND THE ELUSIVE 6.85 μm BAND

The 6.85 {mu}m band observed in the spectra of young stellar objects has been analyzed recently and the most usually accepted assignment to the nu{sub 4} bending mode of NH{sub 4} {sup +} is still under debate. We present here a laboratory study of frozen solutions of NH{sub 4} {sup +}Cl{sup -} in water in an astrophysical range of concentrations and temperatures. The samples are prepared by hyper-quenching of liquid droplets on a cold substrate. The nu{sub 4} band of NH{sub 4} {sup +}, which is very strong in the pure crystal and in the liquid solution at ambient temperature, becomes almost blurred in IR spectra of the frozen solution. The effect of the chlorine anion is expected to be of little relevance in this study. The experimental results are supported by theoretical calculations, which predict a broad range of weak nu{sub 4} features for amorphous samples containing different ammonium environments. The present results indicate that the ammonium ion surrounded by water molecules only cannot suffice to explain this spectral feature. This paper contributes with new evidence to the discussion on the assignment of the 6.85 {mu}m band.

Theoretical Study on Hydrogen-Bond Effects in IR Spectra of High- and Low-Temperature Phases of Nitric Acid Dihydrate

The low- and high-temperature phases (alpha and beta, respectively) of solid nitric acid dihydrate (NAD) are studied in depth by DFT methods. Each phase contains two types of complex structures (H(3)O(+)) x (H(2)O), designated A and B, with different hydrogen-bonding (HB) characteristics. The theoretical study reveals that type A complexes are weakly bound and could be described as (H(3)O)(+) and H(2)O aggregates, with decoupled vibrational modes, whereas in type B structures the proton is situated close to the centre of the O...O bond and induces strong vibrational coupling. The proton-transfer mode is predicted at quite different wavenumbers in each complex, which provides an important differentiating spectral feature, together with splitting of some bands in beta-NAD. Theoretical spectra are estimated by using two GGA parameterizations, namely, PBE and BLYP. The potential-energy surface for each type of HB in NAD is also studied, as is the spectral influence of displacement of the shared H atom along the O-O bond. The results are compared to literature infrared spectra recorded by different techniques, namely, transmission and reflection-absorption, with both normal and tilted incident radiation. This work provides a thorough assignment of the observed spectra, and predictions for some spectra not yet available. The usefulness of high-level theoretical calculations as performed herein to discriminate between two phases of a solid crystal is thus evidenced.