Tailoring electronic and optical properties of TiO2: nanostructuring, doping and molecular-oxide interactions

Titanium dioxide is one of the most widely investigated oxides. This is due to its broad range of applications, from catalysis to photocatalysis to photovoltaics. Despite this large interest, many of its bulk properties have been sparsely investigated using either experimental techniques or ab initio theory. Further, some of TiO2's most important properties, such as its electronic band gap, the localized character of excitons, and the localized nature of states induced by oxygen vacancies, are still under debate. We present a unified description of the properties of rutile and anatase phases, obtained from ab initio state of the art methods, ranging from density functional theory (DFT) to many body perturbation theory (MBPT) derived techniques. In so doing, we show how advanced computational techniques can be used to quantitatively describe the structural, electronic, and optical properties of TiO2 nanostructures, an area of fundamental importance in applied research. Indeed, we address one of the main challenges to TiO2-photocatalysis, namely band gap narrowing, by showing how to combine nanostructural changes with doping. With this aim we compare TiO2's electronic properties for 0D clusters, 1D nanorods, 2D layers, and 3D bulks using different approximations within DFT and MBPT calculations. While quantum confinement effects lead to a widening of the energy gap, it has been shown that substitutional doping with boron or nitrogen gives rise to (meta-)stable structures and the introduction of dopant and mid-gap states which effectively reduce the band gap. Finally, we report how ab initio methods can be applied to understand the important role of TiO2 as electron-acceptor in dye-sensitized solar cells. This task is made more difficult by the hybrid organic-oxide structure of the involved systems.Comment: 32 pages, 8 figure

Renormalization of Optical Excitations in Molecules near a Metal Surface

The lowest electronic excitations of benzene and a set of donor-acceptor molecular complexes are calculated for the gas phase and on the Al(111) surface using the many-body Bethe-Salpeter equation (BSE). The energy of the charge-transfer excitations obtained for the gas phase complexes are found to be around 10% lower than the experimental values. When the molecules are placed outside the surface, the enhanced screening from the metal reduces the exciton binding energies by several eVs and the transition energies by up to 1 eV depending on the size of the transition-generated dipole. As a striking consequence we find that close to the metal surface the optical gap of benzene can exceed its quasiparticle gap. A classical image charge model for the screened Coulomb interaction can account for all these effects which, on the other hand, are completely missed by standard time-dependent density functional theory.Comment: 4 pages, 3 figures; revised versio

Analytical model of non-Markovian decoherence in donor-based charge quantum bits

We develop an analytical model for describing the dynamics of a donor-based charge quantum bit (qubit). As a result, the quantum decoherence of the qubit is analytically obtained and shown to reveal non-Markovian features: The decoherence rate varies with time and even attains negative values, generating a non-exponential decay of the electronic coherence and a later recoherence. The resulting coherence time is inversely proportional to the temperature, thus leading to low decoherence below a material dependent characteristic temperature.Comment: 19 pages, 3 figure

Graphene on metals: a Van der Waals density functional study

We use density functional theory (DFT) with a recently developed van der Waals density functional (vdW-DF) to study the adsorption of graphene on Al, Cu, Ag, Au, Pt, Pd, Co and Ni(111) surfaces. In constrast to the local density approximation (LDA) which predicts relatively strong binding for Ni,Co and Pd, the vdW-DF predicts weak binding for all metals and metal-graphene distances in the range 3.40-3.72 \AA. At these distances the graphene bandstructure as calculated with DFT and the many-body G$_0$W$_0$ method is basically unaffected by the substrate, in particular there is no opening of a band gap at the $K$-point.Comment: 4 pages, 3 figure

Entanglement of formation for a class of (2⊗d)(2\otimes d)-dimensional systems

Currently the entanglement of formation can be calculated analytically for mixed states in a $(2\otimes2)$-dimensional Hilbert space. For states in higher dimensional Hilbert space a closed formula for quantifying entanglement does not exist. In this regard only entanglement bounds has been found for estimating it. In this work, we find an analytical expression for evaluating the entanglement of formation for bipartite ($2\otimes d$)-dimensional mixed states.Comment: 5 pages, 4 figures. Submitted for publicatio

An efficient parametric algorithm for octree traversal

An octree is a well known hierarchical spatial structure which is widely used in Computer Graphics algorithms. One of the most frequent operations is the computation of the octree voxels intersected by a straight line. This has a number of applications, such as ray-object intersection tests speed-up and visualisation of hierarchical density models by ray-casting. Several methods have been proposed to achieve this goal, which differ in the order in which intersected voxels are visited. In this paper we introduce a new top-down parametric method. The main difference with previously proposed methods is related to descent movements, that is, the selection of a child sub-voxel from the current one. This selection, as the algorithm, is based on the parameter of the ray and comprises simple comparisons. The resulting algorithm is easy to implement, and efficient when compared to other related top-down and bottom-up algorithms for octrees. Finally, a comparison with Kelvin’s method for binary trees is presented