2,541 research outputs found
Accuracy of dielectric-dependent hybrid functionals in the prediction of optoelectronic properties of metal oxide semiconductors: a comprehensive comparison with many-body GW and experiments
Understanding the electronic structure of metal oxide semiconductors is crucial to their numerous technological applications, such as photoelectrochemical water splitting and solar cells. The needed experimental and theoretical knowledge goes beyond that of pristine bulk crystals, and must include the effects of surfaces and interfaces, as well as those due to the presence of intrinsic defects (e.g. oxygen vacancies), or dopants for band engineering. In this review, we present an account of the recent efforts in predicting and understanding the optoelectronic properties of oxides using ab initio theoretical methods. In particular, we discuss the performance of recently developed dielectric-dependent hybrid functionals, providing a comparison against the results of many-body GW calculations, including G 0 W 0 as well as more refined approaches, such as quasiparticle self-consistent GW. We summarize results in the recent literature for the band gap, the band level alignment at surfaces, and optical transition energies in defective oxides, including wide gap oxide semiconductors and transition metal oxides. Correlated transition metal oxides are also discussed. For each method, we describe successes and drawbacks, emphasizing the challenges faced by the development of improved theoretical approaches. The theoretical section is preceded by a critical overview of the main experimental techniques needed to characterize the optoelectronic properties of semiconductors, including absorption and reflection spectroscopy, photoemission, and scanning tunneling spectroscopy (STS)
Cerium-doped zirconium dioxide, a visible-light-sensitive photoactive material of third generation
The dispersion of small amounts of Ce4+ ions in the bulk of ZrO2 leads to a photoactive material sensitive to visible light. This is shown by monitoring with EPR the formation and the reactivity of photogenerated (lambda > 420 nm) charge carriers. The effect, as confirmed by DFT calculations, is due to the presence in the solid of empty 4f Ce states at the mid gap, which act as intermediate levels in a double excitation mechanism. This solid can be considered an example of a third-generation photoactive material
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Surface and interstitial Ti diffusion at the rutile TiO2(110) surface
Diffusion of Ti through the TiO2 (110) rutile surface plays a key role in the growth and reactivity of TiO2. To understand the fundamental aspects of this important process, we present an analysis of the diffusion of Ti adspecies at the stoichiometric TiO2(110) surface using complementary computational methodologies of density functional theory corrected for on-site Coulomb interactions (DFT+U) and a charge equilibration (QEq) atomistic potential to identify minimum energy pathways. We find that diffusion of Ti from the surface to subsurface (and vice versa) follows an intersticialcy exchange mechanism, involving exchange of surface Ti with the 6-fold coordinated Ti below the bridging oxygen rows. Diffusion in the subsurface between layers also follows an interstitialcy mechanism. The diffusion of Ti is discussed in light of continued attempts
to understand the re-oxidation of non-stoichiometric TiO2(110) surfaces
Light driven water oxidation by a single site cobalt salophen catalyst
A salophen cobalt(II) complex enables water oxidation at neutral pH
in photoactivated sacrificial cycles under visible light, thus confirming
the high appeal of earth abundant single site catalysis for artificial
photosynthesis
A Medium-Resolution Near-Infrared Spectral Library of Late Type Stars: I
We present an empirical infrared spectral library of medium resolution
(R~2000-3000) H (1.6 micron) and K (2.2 micron) band spectra of 218 red stars,
spanning a range of [Fe/H] from ~-2.2 to ~+0.3. The sample includes Galactic
disk stars, bulge stars from Baade's window, and red giants from Galactic
globular clusters. We report the values of 19 indices covering 12 spectral
features measured from the spectra in the library. Finally, we derive
calibrations to estimate the effective temperature, and diagnostic
relationships to determine the luminosity classes of individual stars from
near-infrared spectra.
This paper is part of a larger effort aimed at building a near-IR spectral
library to be incorporated in population synthesis models, as well as, at
testing synthetic stellar spectra.Comment: 34 pages, 12 figures; accepted for publication at ApJS; the spectra
are available from the authors upon reques
Quasiparticle interfacial level alignment of highly hybridized frontier levels: HO on TiO(110)
Knowledge of the frontier levels' alignment prior to photo-irradiation is
necessary to achieve a complete quantitative description of HO
photocatalysis on TiO(110). Although HO on rutile TiO(110) has been
thoroughly studied both experimentally and theoretically, a quantitative value
for the energy of the highest HO occupied levels is still lacking. For
experiment, this is due to the HO levels being obscured by hybridization
with TiO(110) levels in the difference spectra obtained via ultraviolet
photoemission spectroscopy (UPS). For theory, this is due to inherent
difficulties in properly describing many-body effects at the
HO-TiO(110) interface. Using the projected density of states (DOS) from
state-of-the-art quasiparticle (QP) , we disentangle the adsorbate and
surface contributions to the complex UPS spectra of HO on TiO(110). We
perform this separation as a function of HO coverage and dissociation on
stoichiometric and reduced surfaces. Due to hybridization with the TiO(110)
surface, the HO 3a and 1b levels are broadened into several peaks
between 5 and 1 eV below the TiO(110) valence band maximum (VBM). These
peaks have both intermolecular and interfacial bonding and antibonding
character. We find the highest occupied levels of HO adsorbed intact and
dissociated on stoichiometric TiO(110) are 1.1 and 0.9 eV below the VBM. We
also find a similar energy of 1.1 eV for the highest occupied levels of HO
when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In
both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than
those estimated from UPS difference spectra, which are inconclusive in this
energy region. Finally, we apply self-consistent QP (scQP1) to obtain
the ionization potential of the HO-TiO(110) interface.Comment: 12 pages, 12 figures, 1 tabl
New Insights into the Mechanism of Visible Light Photocatalysis
ABSTRACT: In recent years, the area of developing visible-lightactive photocatalysts based on titanium dioxide has been enormously investigated due to its wide range of applications in energy and environment related fields. Various strategies have been designed to efficiently utilize the solar radiation and to enhance the efficiency of photocatalytic processes. Building on the fundamental strategies to improve the visible light activity of TiO2-based photocatalysts, this Perspective aims to give an insight into many contemporary developments in the field of visible-light-active photocatalysis. Various examples of advanced TiO2 composites have been discussed in relation to their visible light induced photoconversion efficiency, dynamics of electron− hole separation, and decomposition of organic and inorganic pollutants, which suggest the critical need for further development of these types of materials for energy conversion and environmental remediation purposes
Antikinetoplastid SAR study in 3-nitroimidazopyridine series: identification of a novel non-genotoxic and potent anti-T. b. brucei hit-compound with improved pharmacokinetic properties
To study the antikinetoplastid 3-nitroimidazo[1,2-a]pyridine pharmacophore, a structure-activity relationship study was conducted through the synthesis of 26 original derivatives and their in vitro evaluation on both Leishmania spp and Trypanosoma brucei brucei. This SAR study showed that the antitrypanosomal pharmacophore was less restrictive than the antileishmanial one and highlighted positions 2, 6 and 8 of the imidazopyridine ring as key modulation points. None of the synthesized compounds allowed improvement in antileishmanial activity, compared to previous hit molecules in the series. Nevertheless, compound 8, the best antitrypanosomal molecule in this series (EC50 = 17 nM, SI = 2650 & E° = -0.6 V), was not only more active than all reference drugs and previous hit molecules in the series but also displayed improved aqueous solubility and better in vitro pharmacokinetic characteristics: good microsomal stability (T1/2 > 40 min), moderate albumin binding (77%) and moderate permeability across the blood brain barrier according to a PAMPA assay. Moreover, both micronucleus and comet assays showed that nitroaromatic molecule 8 was not genotoxic in vitro. It was evidenced that bioactivation of molecule 8 was operated by T. b. brucei type 1 nitroreductase, in the same manner as fexinidazole. Finally, a mouse pharmacokinetic study showed that 8 displayed good systemic exposure after both single and repeated oral administrations at 100 mg/kg (NOAEL) and satisfying plasmatic half-life (T1/2 = 7.7 h). Thus, molecule 8 appears as a good candidate for initiating a hit to lead drug discovery program
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