Optoelectronics and defect levels in hydroxyapatite by first-principles.

Hydroxyapatite (HAp) is an important component of mammal bones and teeth, being widely used in prosthetic implants. Despite the importance of HAp in medicine, several promising applications involving this material (e.g., in photo-catalysis) depend on how well we understand its fundamental properties. Among the ones that are either unknown or not known accurately, we have the electronic band structure and all that relates to it, including the bandgap width. We employ state-of-the-art methodologies, including density hybrid-functional theory and many-body perturbation theory within the dynamically screened single-particle Green's function approximation, to look at the optoelectronic properties of HAp. These methods are also applied to the calculation of defect levels. We find that the use of a mix of (semi-)local and exact exchange in the exchange-correlation functional brings a drastic improvement to the band structure. Important side effects include improvements in the description of dielectric and optical properties not only involving conduction band (excited) states but also the valence. We find that the highly dispersive conduction band bottom of HAp originates from anti-bonding σ* states along the ⋯OH-OH-⋯ infinite chain, suggesting the formation of a conductive 1D-ice phase. The choice of the exchange-correlation treatment to the calculation of defect levels was also investigated by using the OH-vacancy as a testing model. We find that donor and acceptor transitions obtained within semi-local density functional theory (DFT) differ from those of hybrid-DFT by almost 2 eV. Such a large discrepancy emphasizes the importance of using a high-quality description of the electron-electron interactions in the calculation of electronic and optical transitions of defects in HAp.

Adsorption Behavior of Cellulose and Its Derivatives toward Ag(I) in Aqueous Medium: An AFM, Spectroscopic, and DFT Study.

The aim of this study was to develop a fundamental understanding of the adsorption behavior of metal ions on cellulose surfaces using experimental techniques supported by computational modeling, taking Ag(I) as an example. Force interactions among three types of cellulose microspheres (native cellulose and its derivatives with sulfate and phosphate groups) and the silica surface in AgNO3 solution were studied with atomic force microscopy (AFM) using the colloidal probe technique. The adhesion force between phosphate cellulose microspheres (PCM) and the silica surface in the aqueous AgNO3 medium increased significantly with increasing pH while the adhesion force slightly decreased for sulfate cellulose microspheres (SCM), and no clear adhesion force was observed for native cellulose microspheres (CM). The stronger adhesion enhancement for the PCM system is mainly attributed to the electrostatic attraction between Ag(I) and the negative silica surface. The observed force trends were in good agreement with the measured zeta potentials. The scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analyses confirmed the presence of silver on the surface of cellulose microspheres after adsorption. This study showed that PCM with a high content of phosphate groups exhibited a larger amount of adsorbed Ag(I) than CM and SCM and possible clustering of Ag(I) to nanoparticles. The presence of the phosphate group and a wavenumber shift of the P-OH vibration caused by the adsorption of silver ions on the phosphate groups were further confirmed with computational studies using density functional theory (DFT), which gives support to the above findings regarding the adsorption and clustering of Ag(I) on the cellulose surface decorated with phosphate groups as well as IR spectra.

A hybrid perturbed-chain SAFT density functional theory for representing fluid behavior in nanopores: mixtures.

The perturbed-chain statistical associating fluid theory (PC-SAFT) density functional theory developed in our previous work was extended to the description of inhomogeneous confined behavior in nanopores for mixtures. In the developed model, the modified fundamental measure theory and the weighted density approximation were used to represent the hard-sphere and dispersion free energy functionals, respectively, and the chain free energy functional from interfacial statistical associating fluid theory was used to account for the chain connectivity. The developed model was verified by comparing the model prediction with molecular simulation results, and the agreement reveals the reliability of the proposed model in representing the confined behaviors of chain mixtures in nanopores. The developed model was further used to predict the adsorption of methane-carbon dioxide mixtures on activated carbons, in which the parameters of methane and carbon dioxide were taken from the bulk PC-SAFT and those for solid surface were determined from the fitting to the pure-gas adsorption isotherms measured experimentally. The comparison of the model prediction with the available experimental data of mixed-gas adsorption isotherms shows that the model can reliably reproduce the confined behaviors of physically existing mixtures in nanopores.

Increased electronic coupling in silicon nanocrystal networks doped with F4-TCNQ.

The modification of the electronic structure of silicon nanocrystals using an organic dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), is investigated using first-principles calculations. It is shown that physisorbed F4-TCNQ molecules have the effect of oxidizing the nanocrystal, attracting the charge density towards the F4-TCNQ-nanocrystal interface, and decreasing the excitation energy of the system. In periodic F4-TCNQ/nanocrystal superlattices, F4-TCNQ is suggested to enhance exciton separation, and in the presence of free holes, to serve as a bridge for electron/hole transfer between adjacent nanocrystals.

Electronic and optical properties of chlorinated silicon nanoparticles.

First-principles calculations are used to investigate the structure, electronic and optical properties of silicon nanocystals with chlorine-passivated surface. The nanocrystals considered were approximately spherical, with diameters between 1.5 and 3.0 nm. We show that the nanocrystals with chlorinated surface have a smaller bandgap, lower optical absorption threshold, and greater ionization energy and electron affinity than hydrogenated silicon nanocrystals of the same size.

Physical binding energies using the electron localization function in 4-hydroxyphenylboronic acid co-crystals with aza donors.

Binding energies are traditionally simulated using cluster models by computation of each synthon for each individual co-crystal former. However, our investigation of the binding strengths using the electron localization function (ELF) reveals that these can be determined directly from the crystal supercell computations. We propose a new modeling protocol for the computation of physical binding energies directly from bulk simulations using ELF analysis. In this work, we establish a correlation between ELF values and binding energies calculated for co-crystals of 4-hydroxyphenylboronic acid (4HPBA) with four different aza donors using density functional theory with varying descriptions of dispersion. Boronic acids are gaining significant interest in the field of crystal engineering, but theoretical studies on their use in materials are still very limited. Here, we present a systematic investigation of the non-covalent interactions in experimentally realized co-crystals. Prior diffraction studies on these complexes have shown the competitive nature between the boronic acid functional group and the para-substituted phenolic group forming heteromeric interactions with aza donors. We determine the stability of the co-crystals by simulating their lattice energies, and the different dispersion descriptions show similar trends in lattice energies and lattice parameters. Our study bolsters the experimental observation of the boronic acid group as a competitive co-crystal former in addition to the well-studied phenolic group. Further research on correlating ELF values for physical binding could potentially transform this approach to a viable alternative for the computation of binding energies.

Study on potassium iso-propylxanthate and its decomposition products: experimental 13C CP/MAS NMR combined with DFT calculations.

Solid-state (13)C NMR is believed to be a valuable tool for studying adsorption and speciation of xanthates on sulfide mineral surfaces, but to do that, model compounds of possible xanthate species need to be investigated. (13)C NMR chemical shift tensors for molecular fragments of potassium iso-propylxanthate and six of its decomposition products have been determined by combining DFT calculations and (13)C CP/MAS NMR experiments. DFT calculations were performed in NWChem using GIAO method for the NMR shielding tensor calculations. The results of the calculations are in good agreement with experimental data. In the -XCYZ moiety (X, Y, Z = O, S), the more sulfur atoms, the more deshielded the chemical shift becomes and the larger the span of the chemical shift tensor. The δ11 principal value has the largest influence on the span, decreasing when the number of sulfur atoms decreases and the number of oxygen atoms increases. The significant differences in chemical shifts make it possible to distinguish between different species and, hence, in future studies, interpret surface speciation. The tensor parameters can also aid in the interpretation.

Infection with Panton-Valentine leukocidin-positive methicillin-resistant Staphylococcus aureus t034.

Panton-Valentine leukocidin (PVL)-positive methicillin-resistant Staphylococcus aureus (MRSA), sequence type 398 is believed to be of animal origin. We report 2 cases of infection due to PVL-positive MRSA, spa type t034, in patients in Sweden who had had no animal contact.

Study of potassium O,O'-Dibutyldithiophosphate combining DFT, 31P CP/MAS NMR and infrared spectroscopy.

Dithiophosphates are used in many different industrial applications. To explain their functions and properties in these applications, a fundamental understanding on a molecular level is needed. Potassium O, O'-Dibutyldithiophosphate and its anion have been investigated by means of a combination of DFT and (31)P CP/MAS NMR and infrared spectroscopy. Several low-energy conformations were studied by DFT. Three different conformations with significantly different torsion angles of the O-C bond relative to the O-P-O plane were selected for further studies of infrared frequencies and (31)P NMR chemical-shift tensors. A good agreement between theoretical and experimental results was obtained, especially when the IR spectra or (31)P chemical shift tensor parameters of all three conformations were added, indicating that, because of the low energy difference between the conformations, the molecules are rapidly fluctuating between them.

Accurate control of the covalent functionalization of single-walled carbon nanotubes for the electro-enzymatically controlled oxidation of biomolecules.

Single-walled carbon nanotubes (SWCNTs) were functionalized by ferrocene through ethyleneglycol chains of different lengths (FcETGn) and the functionalized SWCNTs (f-SWCNTs) were characterized by different complementary analytical techniques. In particular, high-resolution scanning electron transmission microscopy (HRSTEM) and electron energy loss spectroscopy (EELS) analyses support that the outer tubes of the carbon-nanotube bundles were covalently grafted with FcETGn groups. This result confirms that the electrocatalytic effect observed during the oxidation of the reduced form of nicotinamide adenine dinucleotide (NADH) co-factor by the f-SWCNTs is due to the presence of grafted ferrocene derivatives playing the role of a mediator. This work clearly proves that residual impurities present in our SWCNT sample (below 5 wt. %) play no role in the electrocatalytic oxidation of NADH. Moreover, molecular dynamic simulations confirm the essential role of the PEG linker in the efficiency of the bioelectrochemical device in water, due to the favorable interaction between the ETG units and water molecules that prevents π-stacking of the ferrocene unit on the surface of the CNTs. This system can be applied to biosensing, as exemplified for glucose detection. The well-controlled and well-characterized functionalization of essentially clean SWCNTs enabled us to establish the maximum level of impurity content, below which the f-SWCNT intrinsic electrochemical activity is not jeopardized.

A theoretical and experimental study of vibrational properties of alkyl xanthates.

Geometrical structure and vibrational modes of potassium and sodium ethyl/heptyl xanthates were studied, using both theoretical and experimental methods. Both Hartree-Fock and density functional theory were used. The experimental method used was infrared absorption spectroscopy (FTIR). Our work showed that vibrational frequencies calculated with density functional theory, using the local density approximation, are in very good agreement with experiments. The results were not improved by using the more sophisticated and computationally demanding B3LYP functional.

Proton transfer reactions for methanol and water containing manganese ion complexes.

Under considerations in the current study are reactions of the type [Mn(LOH)(2)](2+) → [Mn(LO)](+) + LOH(2)(+), where the ligand LOH represents water or/and methanol. Preferential proton transfer reactions and loss of any ligand fragments are discussed in the light of ligand polarizability, dipole moment, dissociation energy, proton affinity, differences in ligand-ion ionization energy, and ion radii. The results indicate the proton affinity and dissociation energy of the O-H bond are more important for the overall proton transfer reaction than differences in the first ionization energy of the ligand and the second ionization energy of the metal ion.

Core structures and kink migrations of partial dislocations in 4H-SiC.

First-principles calculations are used to investigate the Shockley partial dislocations in 4H-SiC. We show that both dislocations can sustain the asymmetric and symmetric reconstructions along the dislocation line. The latter reconstructions are always electrically active. In particular, the Si(g) 30 degrees partials can explain the optical activation energy for the dislocation glide at -2.4 eV above the VB, the narrow peak at 2.87 eV and the broadband at -1.8 eV found in photoluminescence spectra. Further, we propose a new model to explain the stability of the symmetric reconstructions and the enhancement of the dislocation velocity in SiC.