A good correlation was obtained between the electronic properties of Cu-doped anatase TiO2 by virtue of both physical chemistry characterization and theoretical calculations. Pure and Cu-doped TiO2 were synthesized. The composition, structural and electronic properties, and the band gap energy were obtained using several techniques. The method of synthesis used produces Cu-doped anatase TiO2, and XRD, XPS and Raman spectroscopy indicate that Cu atoms are incorporated in the structure by substitution of Ti atoms, generating a distortion of the structure and oxygen vacancies. In turn, the band gap energy of the synthesized samples decrease drastically with the Cu doping. Moreover, periodic density functional theory (DFT-periodic) calculations were carried out both to model the experimentally observed doped structures and to understand theoretically the experimental structures obtained, the formation of oxygen vacancies and the values of the band gap energy. From the analysis of density of states (DOS), projected density of states (PDOS) and the electron localization function (ELF) a decrease in the band gap is predicted upon increasing the Cu doping. Thus, the inclusion of Cu in the anatase structure implies a covalent character in the Cu-O interaction, which involves the appearance of new states in the valence band maximum with a narrowing in the band gap.
A new software (UCA-FUKUI) has been developed to facilitate the theoretical study of chemical reactivity. This program can calculate global parameters like hardness, softness, philicities, and Fukui condensed functions, and also local parameters from the condensed functions. To facilitate access to the program we have developed a very easy-to-use interface. We have tested the performance of the software by calculating the global and local reactivity indexes of a group of representative molecules. Finite difference and frontier molecular orbital methods were compared and their correlation tested. Finally, we have extended the analysis to a set of ligands of importance in coordination chemistry, and the results are compared with the exact calculation. As a general trend, our study shows the existence of a high correlation between global parameters, but a weaker correlation between local parameters.
A previous study presented a very
simple model mainly based on
Sanderson’s principle for estimating important reactivity descriptors,
such as the local hardness and the local electrophilicity. In another
study, a new way of calculating the Fukui function was obtained that
resulted in a new operative formula for the function. We also obtained
the second-order partial derivative of the electron density with regard
to the number of electrons. The current study analyzes the relationships
between the two models and justifies the origin of these relationships.
Aiming for the introduction of stability requirements in nanofluids processing, an interface-based three-step method is proposed in this work. It is theory-based design framework for nanofluids that aims for a minimum tension at the solid-liquid interface by adjusting the polar and dispersive components of the base fluid to meet those of disperse nanomaterial. The method was successfully tested in the preparation of aqueous nanofluids containing single-walled carbon nanotubes that resulted to be stable and to provide good thermal properties, i.e. thermal conductivity increases by 79.5% and isobaric specific heat by 8.6% for a 0.087 vol.% load of nanotubes at 70 °C. Besides, a system for these nanofluids was modelled. It was found to be thermodynamically consistent and computationally efficient, providing consistent response to changes in the state variable temperature in a classical Molecular Dynamics environment. From an analysis of the spatial components of the heat flux autocorrelation function, using the equilibrium approach, it was possible to elucidate that heat conduction through the host fluid is enhanced by phonon propagation along nanotubes longitudinal axes. From an analysis of the structural features described by radial distribution functions, it was concluded that additional heat storage arises from the hydrophobic effect.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.