Tuning the electronic, photophysical and charge transfer properties of small D-A molecules based on Thienopyrazine-terthienyls by changing the donor fragment: A DFT study

Indexación: Scopus.Four acceptor-donor organic conjugated molecules based on thieno[3,4-b]pyrazine-terthienyls were analyzed in order to explore the effect of the donor substituent on their molecular structures, electronic and optical properties. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD/DFT) calculations were carried out employing the B3LYP hybrid functional in combination with the 6-31G(d,p) basis set. The results suggests that the addition of electron-donating substituents to the conjugated molecules can diminish their energy gap value, which is beneficial to the photon harvesting. The lowest-lying absorption spectra of compounds substituted with electron donor groups exhibited a red-shift and a high oscillation factor compared with the unsubstituted molecule. Additionally, the ionization potential (IP), electron affinity (EA), reorganization energy (λ) and open-circuit voltage (Voc) of the molecules were evaluated. According to these values, the molecules show good photovoltaic properties, and efficient charge transfer for hole and electron and balanced charges.https://scielo.conicyt.cl/scielo.php?script=sci_arttext&pid=S0717-97072017000303637&lng=en&nrm=iso&tlng=e

Optoelectronic properties of triphenylamine based dyes for solar cell applications. A DFT study

Indexación: Scopus.GSM thanks to the Department of Chemistry at the Universidad Andres Bello, Concepcion, Chile. LHMH gratefully acknowledges financial support from CONACYT (Projects CB2015-257823) and to the Universidad Autónoma del Estado de Hidalgo.Dye-sensitized solar cells (DSSCs) based on triphenylamine (TPA) as a donor group linked with the acceptor cyanoacrylic acid electron acceptor by 2,2'-bithiophene as π-bridged (D-π-A) has been investigated by Density Functional Theory (DFT) at the B3LYP/6-311G(d,p) level of theory, to establish the conformational orientation of cyanoacrylic acid group as well as evaluate the effect of planarizing the 2,2'-bithiophene unit in position 3 and 3' by electron withdrawing or donor groups on the electronic structure properties of ground and doping(n,p) states. Also, the Time Dependent Density Functional Theory (TD-DFT) at the CPCM-TD-CAM-B3LYP//CAM-B3LYP/6-311G(d,p) level of theory were selected to modulate the electronic absorption spectra and charge-transfer capabilities of the molecules analyzed in the present work. The results indicate that adding an auxiliary donor or withdrawing group to the 2,2'-bithiophene in the (D-π-A) arrangement allow to modify the LUMO's energy of the dyes, while the HOMO's energy is slightly affected. © 2018 Sociedade Brasileira de Quimica. All rights reserved.http://quimicanova.sbq.org.br/imagebank/pdf/AR20170232.pd

Influence of the molecular interaction in the value of molecular volume for the isotropicnematic transition of p-azoxianisol using th emodel HERSW in conjuntion with IPCM model

In this work, we analyzed the experimental pressure-temperature behavior in the Isotropic-Nematic phase transitionfor the liquid crystal p-azoxianisol at 1 atm using a development for the HERSW Conveg Peg model. Additionally, we obtained the values of the molecular volumes for the hard and attractive cores from theoretical quantum calculations at PM3, PM6 and B3LYP/6-311++G levels considering the molecular interaction among the liquidcrystals (PAA)5. We found that the best prediction for experimental data appears when the effect of the molecular interaction is considered in the volume calculation. Specifically for a/b=3.7, V0=70.86 A3 and a/bl=1.95 the best prediction was obtained

Analysis of the Influence of the Molecular Volume to Predict Experimental Pressure-Temperature Behavior in the Isotropic-Nematic Phase Transition of PAP, 5CB, MBBA and EBBA

In this work, we have analyzed the experimental pressure-temperature behavior at the isotropic-nematic phase transition of the liquid crystals PAP, 5CB, MBBA, and EBBA at 1 atm by using the HERSW Convex Peg model in conjunction with the IPCM model. We have calculated the molecular volume values for the hard and attractive cores from theoretical quantum calculations at the PM3, PM6, B3LYP/6-311++G(d,p)//PM6, and M06/6-311++G(d,p)//PM6 levels of theory. The results suggest that the best theoretical prediction of the experimental pressure-temperature behavior is obtained when the molecular volume is evaluated at the DFT level.En este trabajo, nosotros analizamos el comportamiento experimental presión-temperatura pa la fase de transición Isotrópica-nemática de los cristales líquidos PAP, 5CB, MBBA, y EBBA a 1 atm usando el modelo HERSW Convex Peg en conjunto con el modelo IPCM. Nosotros calculamos el valor del volumen molecular y cálculos teóricos para los niveles PM3, PM6, B3LyP/6-311++G(d,p)//PM& y M06/6-311++(d,p)//PM6. Los resultados sugieren que la mejor predicción del comportamiento experimental presión-temperatura es obtenido cuando el volumen molecular es evaluado para el nivel DFT

A DFT Study on the Efficacy of Linking Agents (Sulfur and Nitrogen) to Connect Trans-azobenzene Sandwiched Between Two Gold Electrodes

Electronic structure calculations were performed to analyze the effectiveness of linking agents (sulfur and nitrogen) in connecting the trans-azobenzene sandwiched between two gold surfaces (Au-atoms). It was analyzed the dynamics of the load carrier and the electronic structure of the molecular backbone by applying an external electric field (EF), also a detailed structural, frontier orbital and natural bond orbital analysis (NBO) were performed. From the NBO analysis, it was possible to predict the path of charge flow in the molecular system. Electrostatic potential mapping allowed us to visualize the charge redistribution in the molecular system caused by the EF application. Our results indicate that when the nitrogen atom is used as a linking agent, the azo group of molecules may enhance their conductivity. This work is licensed under a Creative Commons Attribution 4.0 International License

Electrochemical study about zinc electrodeposition onto GCE and HOPG substrates

We carried out an electrochemical study about zinc electrodeposition onto GCE and HOPG substrates from an electrolytic plating bath containing 0.01M ZnSO4 + 1M (NH4)2SO4 at pH 7. Under our experimental conditions the predominant chemical species was the complex [ZnSO4(H2O)5]. The chronoamperometric study showed that zinc electrodeposition follows a typical 3D nucleation mechanism in both substrates. The average dG calculated for the stable nucleus formation was 6.92 x 10-21 J nuclei"1 and 1.35 x 10-20 J nuclei"1 for GCE and HOPG, respectively. The scanning electron microscopy (SEM) images showed different nucleation and growth processes on GCE and HOPG substrates at same overpotential

Influence of Bitartrate Ion Concentration in the Copper Electrodeposition Onto a Polycrystalline Gold Electrode

In the present work, the influence of the concentration of bitartrate ions (HT) on the copper electrodeposition process was analyzed. The study was carried out from an aqueous solution containing 0.001 M of CuX (where X = (NO3–)2 ,(Cl–)2, SO42–) and x M KHT (where x = 0.005 M, 0.01 M, and 0.015 M). From voltammetric and chronoamperometric studies, the results indicate that copper electrodeposition is a diffusion-controlled process. The current density transients were well described through a kinetic mechanism involving capacitive and faradaic contributions. The diffusion coefficient values of Cu1+ and Cu2+ result to be similar at the different concentration values of potassium bitartrate used in this work. This work is licensed under a Creative Commons Attribution 4.0 International License

Kinetical study about the cobalt electrodeposition onto polycrystalline platinum

An electrochemical study of Co electrodeposition onto polycrystalline Pt from an aqueous solution containing 10-2 M CoCl2 + 1 M NH4CI (pH = 9.3) was conducted at overpotential conditions. The current density transients showed two maxima that corresponded to two nucleation and growth processes. The entire transient behavior was adequately predicted considering the contribution to the total current of four different processes: a Langmuir-type adsorption process, a diffusion-controlled two-dimensional instantaneous nucleation, and two three-dimensional nucleation and growth processes

An In Silico Approach to Enzymatic Synthesis of Fucooligosaccharides Using α-L-Fucosidase from Thermotoga maritima

Abstract: Fucooligosaccharides comprise the primary group of human milk oligosaccharides. Due to their beneficial properties, a series of synthetic methods have been proposed to obtain them. Enzy- matic methods show great promise, and α-L-fucosidase from Thermotoga maritima has emerged as a powerful catalyst for their production. Nonetheless, the enzyme’s limited substrate scope has de- layed its wider application. The present work aims to compare the relative reactivity of fucose, pNP-fucose, and ethyl-fucose, while also exploring the molecular interactions of these fucosyl-donors with the enzyme through a combination DFT and docking analysis. The HOMO-LUMO band gaps range from −7.14571 to −4.24429 eV, with α/β-pNP-fucose and α-fucose being the three most reactive compounds. Moderate association energies between −6.4 to −5.5 kcal·mol−1 were found in the dock- ing analysis, with α-pNP-fucose and both anomers of ethyl-fucose demonstrating the poorest affinity. In the case of α/β-lactose affinity to the β-fucose/enzyme complex, no significant differ- ences were shown. We conclude that the best fucosyl-donors for transfucosylation are those that maintain an enzyme affinity and reactivity similar to pNP-fucose

Estudio de factibilidad y propuesta de un proceso de gestión que permita implementar el b-learning en la asignatura Electroquímica.

En este trabajo se reportan los resultados obtenidos mediante una investigación de tipo cuantitativo, enfocada a identificar y reconocer los estilos de aprendizaje y las competencias digitales que poseen los alumnos que se inscriben en el curso denominado Electroquímica; y que se imparte dentro de la Licenciatura en Química en la Universidad Autónoma del Estado de Hidalgo. La información necesaria se recolectó mediante la aplicación de encuestas elaboradas en este trabajo. Al analizar las competencias digitales de los estudiantes se encontró que la totalidad de ellos emplean los teléfonos inteligentes para comunicarse, continuamente navegan en internet con fines didácticos, recreativos y ocupacionales, emplean de manera básica los procesadores de textos, hojas de cálculo y presentaciones electrónicas