Range separated hybrid exchange-correlation functional analyses of W and/or N(S) (co)doped anatase TiO_2

Electronic properties and atomic structures of W, N, S, W/N, and W/S dopings of anatase TiO_2 have been systematically investigated using the density functional theory (DFT). The exchange and correlation effects have been treated with Heyd, Scuseria and Ernzerhof (HSE) hybrid functional. Mixing traditional semi-local and non-local screened Hartree-Fock (HF) exchange energies, the HSE method corrects the band gap and also improves the description of anion/cation derived gap states. Enhanced charge carrier dynamics, observed for W/N codoped titania, can partly be explained by the passivative modifications of N 2p and W 5d states on its electronic structure. Following this trend we have found an apparent band gap narrowing of 1.03 eV for W/S codoping. This is due to the large dispersion of S 3p states at the valance band (VB) top extending its edge to higher energies and Ti--S--W hybridized states appearing at the bottom of the conduction band (CB). W/S-TiO_2 might show strong visible light response comparable to W/N codoped anatase catalysts.Comment: 8 pages, 5 figures and 3 table

A Density Functional Theory Investigation of Carboranethiol Self-Assembled Monolayer on Au(111)

Isolated and full monolayer adsorption of various carboranethiol (C$_2$B$_{10}$H$_{12}$S) isomers on gold (111) surface have been investigated using both the standard and van der Waals density functional theoretical calculations. The effect of differing molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers have been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, the (5$\times$5) was found to be more stable than the ($\sqrt{19}\times\sqrt{19}$)R23.4$^o$ one.Comment: 22 pages, 6 figures and 3 table

Re-assigning (1x2) reconstruction of rutile TiO_2(110) from DFT+U calculations

Physically reasonable electronic structures of reconstructed rutile TiO_2(110)-(1x2) surfaces were studied using density functional theory (DFT) supplemented with Hubbard U on-site Coulomb repulsion acting on the d electrons, so called as the DFT+U approach. Two leading reconstruction models proposed by Onishi--Iwasawa and Park et al. were compared in terms of their thermodynamic stabilities.Comment: 4 pages, 4 figures, 2 table

Dispersion Corrected DFT Study of Pentacene Thin Films on Flat and Vicinal Au Surfaces

Here we a present a density functional theory study of pentacene ultra-thin films on flat [(111)] and vicinal [(455)] Au surfaces. We have performed crystal and electronic structure calculations by using PBE and optB86b-vdW functionals and investigated the effects of long range Van der Waals interactions for different coverages starting from a single isolated molecule up to 4 monolayers of coverage. For an isolated molecule both functionals yield the hollow site as the most stable one with bridge-60 site being very close in energy in case of optB86b-vdW. Binding strength of an isolated pentacene on the step edge was found to be much larger than that on the terrace sites. Different experimentally reported monolayer structures were compared and the (6 x 3) unit cell was found to be energetically more stable than the (2 x 2 $\sqrt{7}$) and (2 x $\sqrt{31}$) ones. For one monolayer films while dispersion corrected calculations favored flat pentacene molecules on terraces, standard (PBE) calculations either found tilted and flat configurations to be energetically similar (on (111) surface) or favored the tilted configuration (on (455) surface). PDOS calculations performed with optB86b-vdW functional showed larger dispersion of molecular orbitals over the Au states for the (455) surface when compared with the (111) surface, indicating an enhanced charge carrier transport at the pentacene-gold interface in favor of the vicinal surface. Starting with the second monolayer, both functionals favored tilted configurations for both surfaces. Our results underline the importance of the dispersion corrections for the loosely bound systems like pentacene on gold and the role played by step edges in determining the multilayer film structure and charge transfer at the organic molecule-metal interface.Comment: 8 Figures, 4 Table

Range separated hybrid density functional study of organic dye sensitizers on anatase TiO2_2 nanowires

The adsorption of organic molecules coumarin and the donor-$\pi$-acceptor type tetrahydroquinoline (C2-1) on anatase (101) and (001) nanowires have been investigated using screened Coulomb hybrid density functional theory calculations. While coumarin forms single bond with the nanowire surface, C2-1 additionally exhibits bidentate mode giving rise to much stronger adsorption energies. Nonlinear solvation effects on the binding characteristics of the dye chromophores on the nanowire facets have also been examined. These two dye sensitizers show different electronic charge distributions for the highest occupied and the lowest unoccupied molecular states. We studied the electronic structures in terms of the positions of the band edges and adsorbate related band gap states and their effect on the absorption spectra of the dye-nanowire combined systems. These findings were interpreted and discussed from the view point of better light harvesting and charge separation as well as in relation to more efficient charge carrier injection into the semiconductor nanowire.Comment: 8 pages, 4 figures, and 1 tabl