Nitrogen sorption as a tool for the characterisation of polysaccharide aerogels

Supercritically dried aerogels of several polysaccharides (chitin, chitosan, alginate, alginic acid, k- carrageenan, and agar) have been characterised by physisorption ofN2. Surface areas as high as 570m2 g−1 have been measured. The nature of the functional groups of the polysaccharide significantly influences the adsorption of N2 on the surface of the aerogel. The net enthalpy of adsorption increases with the polarity of the surface groups of the polymer, in the order chitin < agar≤chitosan < carrageenan < alginic acid∼alginate. The surface area and the mesopore distribution of the aerogels depend both on the dispersion of the parent hydrogel and on the behaviour of each polymer in the drying treatment. Aerogels which retain the dispersion of the parent hydrogel are mainly macroporous (pores larger than 50 nm) while materials liable to shrink upon solvent exchange form mesoporous structures

Electron Nuclear Double Resonance of the Chlorophyll Triplet State in the Water-Soluble Chlorophyll Protein from Brassica oleracea: Investigation of the Effect of the Binding Site on the Hyperfine Couplings

An investigation of the photoexcited triplet state of chlorophyll (Chl) a in the water-soluble chlorophyll protein (WSCP) of Brassica oleracea has been carried out by means of electron-nuclear double resonance (ENDOR), achieving a complete assignment of the observed hyperfine couplings corresponding to methine protons and methyl groups of Chl a triplet state. The triplet-state properties, and in particular the hyperfine couplings, were found to be similar to those previously reported for Chl a in the WSCP of Lepidium virginicum. Therefore, the porphyrin ring deformation observed in Brassica oleracea WSCP seems to only slightly affect the spin density of 3Chl a. This may be relevant when considering the robustness of triplet\u2013triplet energy transfer mechanisms, relying on wavefunction overlap, in systems, such as the photosynthetic light-harvesting complexes, in which Chl triplet states with distorted geometries are involved

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)

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

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 &gt; 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

Nitrogen doping of TiO2 photocatalyst forms a second eg state in the Oxygen (1s) NEXAFS pre-edge

Close inspection of the pre-edge in oxygen near-edge x-ray absorption fine structure spectra of single step, gas phase synthesized titanium oxynitride photocatalysts with 20 nm particle size reveals an additional eg resonance in the VB that went unnoticed in previous TiO2 anion doping studies. The relative spectral weight of this Ti(3d)-O(2p) hybridized state with respect to and located between the readily established t2g and eg resonances scales qualitatively with the photocatalytic decomposition power, suggesting that this extra resonance bears co-responsibility for the photocatalytic performance of titanium oxynitrides at visible light wavelengths

Coupling of hard dimers to dynamical lattices via random tensors

We study hard dimers on dynamical lattices in arbitrary dimensions using a random tensor model. The set of lattices corresponds to triangulations of the d-sphere and is selected by the large N limit. For small enough dimer activities, the critical behavior of the continuum limit is the one of pure random lattices. We find a negative critical activity where the universality class is changed as dimers become critical, in a very similar way hard dimers exhibit a Yang-Lee singularity on planar dynamical graphs. Critical exponents are calculated exactly. An alternative description as a system of `color-sensitive hard-core dimers' on random branched polymers is provided.Comment: 12 page

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

Communication : Hole localization in Al-doped quartz SiO2 within ab initio hybrid-functional DFT

We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO2, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators

Revisiting random tensor models at large N via the Schwinger-Dyson equations

The Schwinger-Dyson Equations (SDEs) of matrix models are known to form (half) a Virasoro algebra and have become a standard tool to solve matrix models. The algebra generated by SDEs in tensor models (for random tensors in a suitable ensemble) is a specific generalization of the Virasoro algebra and it is important to show that these new symmetries determine the physical solutions. We prove this result for random tensors at large N. Compared to matrix models, tensor models have more than a single invariant at each order in the tensor entries and the SDEs make them proliferate. However, the specific combinatorics of the dominant observables allows to restrict to linear SDEs and we show that they determine a unique physical perturbative solution. This gives a new proof that tensor models are Gaussian at large N, with the covariance being the full 2-point function.Comment: 17 pages, many figure