ABSTRACT
The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.
ABSTRACT
In this work, we present a theoretical study of the electronic properties of group-IV element nanosheets, namely graphene, silicene, germanene and the corresponding hydrogenated structures for the two latter, silicane and germanane. We compare the results of two different calculation methods, Density Functional Theory (DFT) and Extended Hückel Theory (EHT), for both pristine sheets and sheets of silicene and germanene with a single-atom vacancy. We show that EHT offers a remarkably reliable description of the electronic structure of these materials for all cases, thus offering an affordable way for studying large systems for which DFT calculations would be expensive and lengthy.
ABSTRACT
We report first-principles characterization of the structural and electronic properties of (SrTiO3)5/(SrRuO3)1 superlattices. We show that the system exhibits a spin-polarized two-dimensional electron gas, extremely confined to the 4d orbitals of Ru in the SrRuO3 layer. Every interface in the superlattice behaves as a minority-spin half-metal ferromagnet, with a magnetic moment of µ=2.0µ(B)/SrRuO3 unit. The shape of the electronic density of states, half-metallicity, and magnetism are explained in terms of a simplified tight-binding model, considering only the t(2g) orbitals plus (i) the bidimensionality of the system and (ii) strong electron correlations.
