A DFT study of the effect of hydrostatic pressure on the structure and electronic properties of sarcosine crystal.

CONTEXT: We perform density functional theory calculations to study the dependence of the structural and electronic properties of the amino acid sarcosine crystal structure on hydrostatic pressure application. The results are analyzed and compared with the available experimental data. Our findings indicate that the crystal structure and properties of sarcosine calculated using the Grimme dispersion-corrected PBE functional (PBE-D3) best agree with the available experimental results under hydrostatic pressure of up to 3.7 GPa. Critical structural rearrangements, such as unit cell compression, head-to-tail compression, and molecular rotations, are investigated and elucidated in the context of experimental findings. Band gap energy tuning and density of state shifts indicative of band dispersion are presented concerning the structural changes arising from the elevated pressure. The calculated properties indicate that sarcosine holds great promise for application in electronic devices that involve pressure-induced structural changes. METHODS: Three widely used generalized gradient approximation functionals-PBE, PBEsol, and revPBE-are employed with Grimme's D3 dispersion correction. The non-local van der Waals density functional vdW-DF is also evaluated. The calculations are performed using the projector-augmented wave method in the Quantum Espresso software suite. The geometry optimization results are visualized using VMD. The Multiwfn and NCIPlot programs are used for wavefunction and intermolecular interaction analyses.

Characterization of NiCuOxNy Coatings Obtained via RF Sputtering: Structure, Morphology, and Optical Properties.

The rapid advancement of technology necessitates the continual development of versatile materials that can adapt to new electronic devices. Rare earth elements, which are scarce in nature, possess the set of properties required for use as semiconductors. Consequently, this research aims to achieve similar properties using materials that are abundant in nature and have a low commercial cost. To this end, nickel and copper were utilized to synthesize thin films of nickel-copper binary oxynitride via reactive RF sputtering. The influence of nitrogen flow on the structure, morphology, chemical composition, and optical properties of the films was investigated using various characterization techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS), as well as transmittance and absorbance measurements. The crystalline structure of the films shows that they can have preferential growth or be polycrystalline according to the nitrogen flow used during deposition and that both the oxides and oxynitrides of metals are formed. We identified unknown phases specific to this material, termed "NiCuOxNy". The morphology revealed that the grain size of the coatings was dependent on the nitrogen flow rate, with grain size decreasing as the nitrogen flow rate increased. Notably, the coatings demonstrated transparency for wavelengths exceeding 1000 nm, with an optical band gap ranging from 1.21 to 1.86 eV.

Gap engineering effects on transport and tunneling magnetoresistance properties in phosphorene ferromagnetic/normal/ferromagnetic junction.

Tuning the band gap is of utmost importance for the practicality of two-dimensional materials in the semiconductor industry. In this study, we investigate the ballistic transport and the tunneling magnetoresistance (TMR) properties within a modulated gap in a ferromagnetic/normal/ferromagnetic (F/N/F) phosphorene junction. The theoretical framework is established on a Dirac-like Hamiltonian, the transfer matrix method, and the Landauer-Büttiker formalism to characterize electron behavior and obtain transmittance, conductance and TMR. Our results reveal that a reduction in gap energy leads to an enhancement of conductance for both parallel and anti-parallel magnetization configurations. In contrast, a significant reduction and redshift in TMR have been observed. Notably, the application of an electrostatic field in a gapless phosphorene F/N/F junction induces a blueshift and a slight increase in TMR. Furthermore, we found that introducing an asymmetrically applied electrostatic field in this gapless junction results in a significant reduction and redshift in TMR. Additionally, intensifying the applied magnetic field leads to a substantial increase in TMR. These findings could be useful for designing and implementing practical applications that require precise control over the TMR properties of a phosphorene F/N/F junction with a modulated gap.

Impacts of dielectric screening on the luminescence of monolayer WSe2.

Single layers of transition metal dichalcogenides (TMDCs), such as WSe2have gathered increasing attention due to their intense electron-hole interactions, being considered promising candidates for developing novel optical applications. Within the few-layer regime, these systems become highly sensitive to the surrounding environment, enabling the possibility of using a proper substrate to tune desired aspects of these atomically-thin semiconductors. In this scenario, the dielectric environment provided by the substrates exerts significant influence on electronic and optical properties of these layered materials, affecting the electronic band-gap and the exciton binding energy. However, the corresponding effect on the luminescence of TMDCs is still under discussion. To elucidate these impacts, we used a broad set of materials as substrates for single-layers of WSe2, enabling the observation of these effects over a wide range of electrical permittivities. Our results demonstrate that an increasing permittivity induces a systematic red-shift of the optical band-gap of WSe2, intrinsically related to a considerable reduction of the luminescence intensity. Moreover, we annealed the samples to ensure a tight coupling between WSe2and its substrates, reducing the effect of undesired adsorbates trapped in the interface. Ultimately, our findings reveal how critical the annealing temperature can be, indicating that above a certain threshold, the heating treatment can induce adverse impacts on the luminescence. Furthermore, our conclusions highlight the influence the dielectric properties of the substrate have on the luminescence of WSe2, showing that a low electrical permittivity favours preserving the native properties of the adjacent monolayer.

Copper oxide nanoparticles doped with lanthanum, magnesium and manganese: optical and structural characterization.

Copper oxide (Cu2O) is a promising semiconductor for photovoltaic and photocatalytic applications since this material has a high optical absorption coefficient and lower band gap (2.17 eV). Doped lanthanum (La), magnesium (Mg) and manganese (Mn) Cu2O nanoparticles (Cu2O Nps) were prepared by a displacement reaction. The doped and undoped Cu2O Nps were characterized with scanning electron microscopy-energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. The EDS results confirm the presence of La, Mg and Mn in the Cu2O Nps. The XRD results confirm the formation a single cubic phase of Cu2O with a cuprite structure. TEM images confirm the formation of Nps with mean diameters between 12.0 ± 6.1 and 30.8 ± 11.0 nm. Doped and undoped Nps present a narrow band gap (2.40 eV), blue shifted with respect to bulk Cu2O.

Reaching Visible Light Photocatalysts with Pt Nanoparticles Supported in TiO2-CeO2.

Nanostructured catalysts of platinum (Pt) supported on commercial TiO2, as well as TiO2-CeO2 (1, 5 and 10 wt% CeO2), were synthesized through the Sol-Gel and impregnation method doped to 1 wt% of Platinum, in order to obtain a viable photocatalytic material able to oxidate organic pollutants under the visible light spectrum. The materials were characterized by different spectroscopy and surface techniques such as Specific surface area (BET), X-ray photoelectron spectroscopy (XPS), XRD, and TEM. The results showed an increase in the diameter of the pore as well as the superficial area of the supports as a function of the CeO2 content. TEM images showed Pt nanoparticles ranking from 2-7 nm, a decrease in the particle size due to the increase of CeO2. The XPS showed oxidized Pt2+ and reduced Pt0 species; also, the relative abundance of the elements Ce3+/Ce4- and Ti4+ on the catalysts. Additionally, a shift in the Eg band gap energy (3.02-2.82 eV) was observed by UV-vis, proving the facticity of applying these materials in a photocatalytic reaction using visible light. Finally, all the synthesized materials were tested on their photocatalytic oxidation activity on a herbicide used worldwide; 2,4-Dichlorophenoxyacetic acid, frequently use in the agriculture in the state of Jalisco. The kinetics activity of each material was measured during 6 h of reaction at UV-Vis 190-400 nm, reaching a removal efficiency of 98% of the initial concentration of the pollutant in 6 h, compared to 32% using unmodified TiO2 in 6 h.

Effect of Ethylene Glycol: Citric Acid Molar Ratio and pH on the Morphology, Vibrational, Optical and Electronic Properties of TiO2 and CuO Powders Synthesized by Pechini Method.

High-purity TiO2 and CuO powders were synthesized by the Pechini method, an inexpensive and easy-to-implement procedure to synthetize metal oxides. The variables of synthesis were the ethylene glycol:citric acid molar ratio and the pH. High reproducibility of the anatase and tenorite phase was obtained for all synthesis routes. The degree of purity of the powders was confirmed by XRD, FTIR, UV-Vis absorption and XPS spectra. SEM and TEM images revealed the powders are composed of micrometer grains that can have a spherical shape (only in the TiO2) or formed by a non-compacted nanocrystalline conglomerate. FTIR spectra only displayed vibrational modes associating TiO2 and CuO with nanoparticle behavior. UV-Vis absorption spectra revealed the values of maximum absorbance percentage of both systems are reached in the ultraviolet region, with percentages above 83% throughout the entire visible light spectrum for the CuO system, a relevant result for solar cell applications. Finally, XPS experiments allow the observation of the valence bands and the calculation of the energy bands of all oxides.

First-principles studies of the strain-induced band-gap tuning in black phosphorene.

Using first-principles calculations, we have studied the band-gap modulation as function of applied strain in black phosphorene (BP). Dynamical stability has been assessed as well. Three cases have been considered, in the first and second, the strain was applied uniaxially, in thex- andy-axis, separately. In the third, an isotropic in-plane strain was analyzed. Different strain percentages have been considered, ranging from 4% to 20%. The evolution of the band-gap is studied by using standard DFT and the G0W0approach. The band-gap increases for small strains but then decreases for higher strains. A change in electronic behavior also takes place: the strained systems change from direct to indirect band-gap semiconductor, which is explained in terms of thesandp-orbitals overlap. Our study shows that BP is a system with a broad range of applications: in band-gap engineering, or as part of van der Waals heterostructures with materials of larger lattice parameters. Its stability, and direct band-gap behavior are not affected for less than 16% of uniaxial and biaxial strain. Our findings show that phosphorene could be deposited in a large number of substrates without losing its semiconductor behavior.

Spectroscopic Properties of Si-nc in SiOx Films Using HFCVD.

In the present work, non-stoichiometric silicon oxide films (SiOx) deposited using a hot filament chemical vapor deposition technique at short time and simple parameters of depositions are reported. This is motivated by the numerous potential applications of SiOx films in areas such as optoelectronics. SiOx films were characterized with different spectroscopic techniques. The deposited films have interesting characteristics such as the presence of silicon nanoclusters without applying thermal annealing, in addition to a strong photoluminescence after applying thermal annealing in the vicinity of 1.5 eV, which may be attributed to the presence of small, oxidized silicon grains (less than 2 nm) or silicon nanocrystals (Si-nc). An interesting correlation was found between oxygen content, the presence of hydrogen, and the formation of defects in the material, with parameters such as the band gap and the Urbach energies. This correlation is interesting in the development of band gap engineering for this material for applications in photonic devices.

Photocatalytic Degradation of Diclofenac Using Al2O3-Nd2O3 Binary Oxides Prepared by the Sol-Gel Method.

This paper reports the sol-gel synthesis of Al2O3-Nd2O3 (Al-Nd-x; x = 5%, 10%, 15% and 25% of Nd2O3) binary oxides and the photodegradation of diclofenac activated by UV light. Al-Nd-based catalysts were analyzed by N2 physisorption, XRD, TEM, SEM, UV-Vis and PL spectroscopies. The inclusion of Nd2O3 in the aluminum oxide matrix in the 10-25% range reduced the band gap energies from 3.35 eV for the γ-Al2O3 to values as low as 3.13-3.20 eV, which are typical of semiconductor materials absorbing in the UV region. γ-Al2O3 and Al-Nd-x binary oxides reached more than 92.0% of photoconverted diclofenac after 40 min of reaction. However, the photocatalytic activity in the diclofenac degradation using Al-Nd-x with Nd2O3 contents in the range 10-25% was improved with respect to that of γ-Al2O3 at short reaction times. The diclofenac photoconversion using γ-Al2O3 was 63.0% at 10 min of UV light exposure, whereas Al-Nd-15 binary oxide reached 82.0% at this reaction time. The rate constants determined from the kinetic experiments revealed that the highest activities in the aqueous medium were reached with the catalysts with 15% and 25% of Nd2O3, and these compounds presented the lowest band gap energies. The experimental results also demonstrated that Nd2O3 acts as a separator of charges favoring the decrease in the recombination rate of electron-hole pairs.

Experimental and DFT Study of the Photoluminescent Green Emission Band of Halogenated (-F, -Cl, and -Br) Imines.

The morphological, optical, and structural changes in crystalline chiral imines derived from 2-naphthaldehyde as a result of changing the -F, -Cl, and -Br halogen (-X) atoms are reported. Scanning electron microscopy (SEM), optical absorption, photoluminescence (PL), and powder X-ray diffraction (XRD) studies were performed. Theoretical results of optical and structural properties were calculated using the PBE1PBE hybrid functional and compared with the experimental results. Differences in surface morphology, absorbance, XRD, and PL of crystals were due to the change of halogen atoms in the chiral moiety of the imine. Absorption spectra exhibited the typical bands of the naphthalene chromophore located in the ~200-350 nm range. Observed absorption bands in the UV region are associated with π→π* and n→π* electronic transitions. The band gap energy was calculated using the Tauc model. It showed a shift in the ~3.5-4.5 eV range and the crystals exhibited different electronic transitions associated with the results of absorbance in the UV region. XRD showed the monoclinic→orthorhombic crystalline phase transition. PL spectra displayed broad bands in the visible region and all the samples have an emission band (identified as a green emission band) in the ~400-750 nm range. This was associated with defects produced in the morphology, molecular packing, inductive effect and polarizability, crystalline phase transition, and increase in size of the corresponding halogen atoms; i.e., changes presumably induced by -C-X…X-, -C-X…N-, -C-N…π, and -C-X…π interactions in these crystalline materials were associated with morphological, optical, and structural changes.

Evaluación teórica de las propiedades electrónicas y estructurales que afectan a la conductividad eléctrica en copolímeros de furano-tiofeno / Theoretical evaluation of the electronic and structural properties that affect the electrical conductivity in furan-thiophene copolymers / Avaliação teórica das propriedades eletrônicas e estruturais que afetam à condutividade eléctrica em copolímeros de furano-tiofeno

Resumen Desde el punto de vista científico y tecnológico ha habido un gran interés en el uso de monosustituyentes de furano y tiofeno como polímeros conductores, debido a sus múltiples aplicaciones como OLED, amplificadores ópticos, nanotecnología, entre otros. Por ello, el propósito de este trabajo fue estudiar los aspectos teóricos que afectan las propiedades electroconductoras de este tipo de moléculas. Se determinaron teóricamente los aspectos estructurales y electrónicos que influyeron en la conductividad de copolímeros de furano-tiofeno monosustituidos, al utilizar grupos carboxilos, metilos, hidroxilos, ciano y fluoruros como sustituyentes en el carbono C3 y C10 de cada heterociclo. La diferencia de energía entre el LUMO y el HOMO (band gap, Eg) y el potencial de ionización (PI) fue calculada a partir de las geometrías optimizadas en DFT para el estado neutro, anión y catión. Los PI y la Eg de los copolímeros fueron obtenidos mediante la extrapolación de los valores del oligómero a (1/N) y de una cadena de longitud infinita (1/N=0), obteniéndose una correlación lineal (R=0,99), la cual se mantiene a lo largo de todos los modelos de ajuste de cada copolímero analizado en el estudio.

Abstract There has been great scientific and technological interest in the use of mono-substituents of furan and thiophene as conducting polymers due to their multiple applications such as OLED, optical amplifiers and nanotechnology, among others. For this, the purpose of this work was to study the theoretical aspects that affect the electroconductive properties of this type of molecules. The structural and electronic properties that influence the conductivity of mono substituted-furan-thiophene copolymers were determined theoretically. The effect of using carboxyl, methyl, hydroxyl, cyano, and fluoride groups as substituents on the carbon C3 and C10 of each heterocycle was observed. The energy difference between the LUMO and the HOMO (band gap, Eg) and the ionization potential (IP) were calculated from the geometries optimized in DFT for the neutral, anion and cation state. The PI and Eg of the copolymers were obtained by extrapolating the values of the oligomer a (1/N) and a chain of infinite length (1/N=0) for which a linear correlation was obtained (R=0.99). This correlation is maintained throughout all the adjustment models of each copolymer analyzed in the study.

Resumo Existe muito interesse os termos científicos e tecnológicos em utilizar substituintes mono-substituídos furano e tiofeno como polímeros condutores devido às suas múltiplas aplicações, tais como OLED, amplificadores ópticos e nanotecnologia, entre outros. O objetivo deste trabalho foi estudar os aspectos teóricos que afetam as propriedades eletrocondutoras deste tipo de moléculas. Neste contribuição os aspectos estruturais e electrónicas que influenciam a condutividade de copolímeros furano-tiofeno substituos mono teoricamente determinada observando o efeito do uso de grupos carboxilo, metilo, hidroxilo, ciano e fluoretos como substituintes em C3 e C10 de carbono de cada heterociclo. A diferença de energia entre o LUMO e o HOMO (intervalo de banda, Eg) e o potencial de ionização (IP) foram calculadas a partir das geometrias optimizadas de DFT para o estado neutro, anião e catião. O PI e o Eg dos copolímeros foram obtidos por extrapolação dos valores do oligómero (1/N) e extrapolando para uma cadeia de comprimento infinito (1/ N=0) para os quais uma correlação linear foi obtida (R=0,99), que é mantido ao longo de todos os modelos de ajuste de cada copolímero analisados no estudo.

Towards visible-light photocatalysis for environmental applications: band-gap engineering versus photons absorption-a review.

A range of different studies has been performed in order to design and develop photocatalysts that work efficiently under visible (and near-infrared) irradiation as well as to improve photons absorption with improved reactor design. While there is consensus on the importance of photocatalysis for environmental applications and the necessity to utilized solar irradiation (or visible-light) as driving force for these processes, it is not yet clear how to get there. Discussion on the future steps towards visible-light photocatalysis for environmental application is of great interest to scientific and industrial communities and the present paper reviews and discusses the two main approaches, band-gap engineering for efficient solar-activated catalysts and reactor designs for improved photons absorption. Common misconceptions and drawbacks of each technology are also examined together with insights for future progress.

Visible light driven photo-degradation of Congo red by TiO2ZnO/Ag: DFT approach on synergetic effect on band gap energy.

In this paper, we report the combination of two metal oxides (TiO2ZnO) that allows mixed density of states to reduce band gap energy, facilitating the photo-oxidation of Congo red dye under visible light. For the oxidation, a possible mechanism is proposed after analyzing the intermediates by GC-MS, and it is consistent with Density Functional Theory (DFT). The nanohybrids were characterized comprehensibly by several analytical techniques such as X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS). For the addition of ZnO to TiO2, a dominance of anatase phase was found rather than other phases (rutile or brookite). A broad band (∼550 nm) is observed in UV-Visible spectra for TiO2ZnO/Ag NPs nm because of Surface Plasmon properties of Ag NPs. The band gap energy was calculated for TiO2ZnO/Ag system, and then it has been further studied by DFT in order to show why the convergence of two semiconductors allows a mixed density of states, facilitating the reduction of the energy gap between occupied and unoccupied bands; ultimately, it improves the performance of catalysts under visible light. Significantly, the interaction of crystal planes (0 0 I) of TiO2 anatase and (0 0 1) of ZnO crucially plays as an important role for the reduction of energy band-gap. Additionally, TiO2ZnOAg NPs were used recognize Saccharomyces cerevisiae cells by con-focal fluorescence microscope, showing that it develops bright bio-images for the cells; while for TiO2 or ZnO or TiO2ZnO NPs, no fluorescent response was seen within the cells.

Photocharging and Band Gap Narrowing Effects on the Performance of Plasmonic Photoelectrodes in Dye-Sensitized Solar Cells.

The incorporation of plasmonic nanostructures in active electrodes has become one of the most attractive ways to enhance the photoconversion efficiency (PCE) of dye-sensitized solar cells (DSSCs). Although an enhancement of PCE because of the incorporation of plasmonic nanostructures of different sizes, either bare or coated, has been demonstrated, the fundamental mechanisms associated to such enhancement are still unclear. Besides, the photocurrent enhancement of plasmonic DSSCs is frequently associated to the strong surface plasmon resonance (SPR) absorption of metal nanoparticles. In this work, through oxygen K-edge soft X-ray absorption and emission spectroscopies of plasmonic electrodes and electrodynamical characterization of the fabricated cells, we demonstrate a band gap narrowing and photocharging effect on the plasmonic electrodes that definitely contribute to the PCE enhancement in plasmonic DSSCs. The incorporation of bare metal nanoparticles in active metal-oxide semiconductor electrodes such as TiO2 in optimum concentration causes an upward shift of its valence band edge, reducing its effective band gap energy and enhancing the short-circuit current of DSSCs. On the other hand, small perturbation-based stepped light-induced transient measurements of photovoltage and photocurrent of the operating DSSCs revealed an upward shift of quasi-Fermi level of photoelectrodes because of the photocharging effect induced by the incorporated metal nanoparticles. The upward shift of the quasi-Fermi level causes an increase in open-circuit voltage ( VOC), nullifying the effect of band gap reduction. The short-circuit photocurrent enhancement was controlled by the band gap narrowing, screening the SPR contribution. The results presented in this work not only clarify the contribution of SPR absorption in plasmonic DSSCs, but also highlight the importance of considering the corrections in the effective base voltage because of the quasi-Fermi level band shift during the estimation of the transport and recombination parameters of an assembled DSSC.

Photonic Crystal Characterization of the Cuticles of Chrysina chrysargyrea and Chrysina optima Jewel Scarab Beetles.

A unified description involving structural morphology and composition, dispersion of optical constants, modeled and measured reflection spectra and photonic crystal characterization is devised. Light reflection spectra by the cuticles of scarab beetles (Chrysina chrysargyrea and Chrysina optima), measured in the wavelength range 300-1000 nm, show spectrally structured broad bands. Scanning electron microscopy analysis shows that the pitches of the twisted structures responsible for the left-handed circularly polarized reflected light change monotonically with depth through the cuticles, making it possible to obtain the explicit depth-dependence for each cuticle arrangement considered. This variation is a key aspect, and it will be introduced in the context of Berreman's formalism, which allows us to evaluate reflection spectra whose main features coincide in those displayed in measurements. Through the dispersion relation obtained from the Helmholtz's equation satisfied by the circular components of the propagating fields, the presence of a photonic band gap is established for each case considered. These band gaps depend on depth through the cuticle, and their spectral positions change with depth. This explains the presence of broad bands in the reflection spectra, and their spectral features correlate with details in the variation of the pitch with depth. The twisted structures consist of chitin nanofibrils whose optical anisotropy is not large enough so as to be approached from modeling the measured reflection spectra. The presence of a high birefringence substance embedded in the chitin matrix is required. In this sense, the presence of uric acid crystallites through the cuticle is strongly suggested by frustrated attenuated total reflection and Raman spectroscopy analysis. The complete optical modeling is performed incorporating the wavelength-dependent optical constants of chitin and uric acid.

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules.

We studied the electronic and conductance properties of two thiophene-curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO-LUMO band gap energies, showing that molecule 1 has lower values than 2. Theoretical calculations show the same trend. Self-assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO-LUMO gap in both molecules to almost the same value. Single-molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.

Synthesis of tunable-band-gap "Open-Box" halide perovskites by use of anion exchange and internal dissolution procedures.

We demonstrate the synthesis of cuboid MAPbBr3 (MA=CH3NH3) microcrystals and subsequent conversion into open-box-like MAPb(Br(1-x)I(x))3 (0⩽x⩽1) microcrystals by anion exchange in MAI solution. During the substitution of Br(-) with I(-), the initial cuboid framework of MAPbBr3 crystals is retained. The preferential internal dissolution of MAPbBr3 due to the surface coverage and protection of MAPb(Br(1-x)I(x))3 induces voids inside the cuboid crystals, finally leading to open-box-like iodide-rich MAPb(Br(1-x)I(x))3. By controlling the degree of anion exchange, the intense light absorption of the product is able to be tuned in specific wavelengths throughout the visible range. This solution-phase anion exchange approach provides a synthetic strategy in designing sophisticated organolead halide perovskites structures as well as tuning the band gaps for further applications across a range of possible domains.

The Band Gap of Graphene Is Efficiently Tuned by Monovalent Ions.

Small monovalent ions are able to polarize carbonaceous nanostructures significantly. We report a systematic investigation of how monovalent and divalent ions influence valence electronic structure of graphene. Pure density functional theory is employed to compute electronic energy levels. We show that the lowest unoccupied molecular orbital (LUMO) of an alkali ion (Li(+), Na(+)) fits between the highest occupied molecular orbital (HOMO) and LUMO of graphene, in such a way as to tune the bottom of the conduction band (i.e., band gap). In turn, Mg(2+) shares its orbitals with graphene. The corresponding binding energy is ca. 4 times higher than that in the case of alkali ions. The reported insights provide inspiration for engineering electrical properties of the graphene-containing systems.

Estudio teóricoppara evaluar la conductividad dl polifurano y el efecto de loss sustituyentes sobre la cadena polimérica / Theoretcal studyy to evaluate polyfuranelectrical conductivity and thee substituent effects on the polymeri cchain / Estud teorico paara avaliar a conductvidade do polifurano o e efeitoo dos substituintes sobre a cadeia polmmerica

Una serie de oligómeros de furano y furano sustituido fueron estudiados desde el punto de vista teórico con el objeto de conocer las propiedades electroconductoras de estos compuestos, y su respectiva extrapolación a polímeros, aprovechando la capacidad de la química computacional para proponer y diseñar nuevos materiales y sus posibles propiedades. Se relacionaron las propiedades electrónicas de estos oligómeros tales como la afinidad electrónica (AE), el potencial de ionización (PI), el band-gap (HOMOLUMO), y la relación de éstos con la conductividad; además, se demostró cómo cambia la longitud de los enlaces de los oligómeros al estar cargados; la longitud de los oligómeros de estudio fuer de dos, cuatro, seis y ocho anillos. En este estudio se realizaron cálculos a niveles AM1 y DFT/B3LYP/6-31G (d).

DFT/B3LYP/6-31G (d) calculations were carried out on a series of molecules of furan and substituted furan to observe the type of variables that affect the conductivity of these molecules. In order to propose and design new molecules and its possible properties. The Ionization potential (IP), band-gap (HOMO-LUMO), electronic affinity (EA), was related with its conductivity. It was also shown how change the length of the olygomers bond when the number of the rings is changed from two to four, six and eight.

Uma serie de oligômeros de furano y furano substituido foram estudados teoricamente com a intenção de conhecer as propriedades electro-conductoras desses compostos e sua respectiva extrapolação a polímeros, aproveitando a capacidade da química computacional para propor e desenhar novos materiais e suas possíveis propriedades. Relacionaram-se as propriedades eletrônicas destes oligômeros, tais como a afinidade eletrônica (AE), o potencial de ionização (PI), o band-gap (HOMO-LUMO) e a relação destes com a condutividade, também se demostrou a mudança do comprimento das ligações dos oligômeros ao estar carregados, o comprimento dos oligômeros em estudo foram de dois, quatro, seis e oito anéis. Em este estudo realizaram-se cálculos a níveis AM1 e DFT/B3LYP/6-31G (d).