Electronic Parameters Research Articles

Characterization and Application of Cyrene as a Biomass-Based Solvent for Homogeneous Heck-Coupling Reaction.

Cyrene, a renewable, non-toxic substance having negligible vapor pressure, even at high temperatures, was proposed as a reaction medium for homogeneous Pd-catalyzed Heck-coupling reactions. It was first characterized by its temperature-dependent physicochemical properties, i.e., vapor pressure, density, surface tension, heat capacity, and viscosity, the key parameters of its reaction and process chemistry. Its refractive indices in the function of temperature were also determined. Hereafter, the effect of reaction parameters (Pd source, nature of the base, the water content of the reaction mixture, leaving group (-I, -Br, -Cl, and -OTf of aromatic substrates) on Pd-catalyzed Heck-coupling reaction was investigated using iodobenzene and styrene as model substrates. Subsequently, 4-substituted iodobenzene and styrene derivatives were applied to investigate the effect of electronic parameters on the reaction efficiency and functional group tolerance. To demonstrate the applicability of the system, thirteen stilbene derivatives were isolated with good to high yields and purity (> 95%) using 0.2 mol% of Pd, 1.5 eq. of Et3N as a base, in 1 mL of Cyrene for 2 h at 100 °C.

Twisted graphene superlattices: resonating valence bond states and magnetic properties

Resonating valence bond (RVB) states are fundamental for understanding quantum spin liquids in two-dimensional (2D) systems. The RVB state is a collective phenomenon in which spins are uncoupled. 2D lattices such as triangular, honeycomb, and dice lattices were investigated using the Hubbard model and exact diagonalization method. We analyzed the total spin, spin–spin correlation functions, local magnetic moments, and spin and charge gaps as a function of on-site Coulomb repulsion, electron concentration, and electronic hopping parameters. Phase diagrams showed that RVB states can live in half-filled and hole-doped anisotropic triangular lattices. We found two types of RVB states: one in the honeycomb sublattice and the other in the centered hexagons in the triangular lattices. Owing to the novel discovery of exotic magnetic ordering in triangular moiré patterns in twisted bilayer graphene and transition metal dichalcogenide systems, our results provide physical insights into the onset of magnetism and possible spin liquid states in these layered materials.

Insights into the optoelectronic and thermoelectric properties of defect chalcopyrites XAl2Se4 (X = Zn, Cd, and Hg): A density functional theory approach

In the current study, we employed the full-potential linearized augmented plane wave plus local orbitals (FP-LAPW + lo) approach within the density functional theory (DFT) to investigate the physical properties of Defect Chalcopyrites XAl2Se4 (X = Zn, Cd, and Hg). Calculations yield precise structural and electronic parameters in good agreement with experimental data, revealing all three compounds as direct wide-bandgap semiconductors. The modified Becke-Johan potential (TB-mBJ) method accurately estimates energy gaps, which increase with decreasing lattice constants. The calculated values are 3.34 eV, 3.12 eV, and 2.30 eV for ZnAl2Se4, CdAl2Se4, and HgAl2Se4, respectively. The optical properties, including dielectric function and absorption coefficient, indicate potential applications in visible and ultraviolet optoelectronic devices. The high anisotropy of these materials further enhances their suitability for a range of linear and nonlinear optical applications. Moreover, ZnAl2Se4 exhibits the highest Seebeck coefficient at room temperature. The positive Seebeck coefficient confirmed the p-type behavior of the studied compounds. The highest observed power factor demonstrates optimal thermoelectric performance for these materials. High electrical conductivity values suggest their suitability as effective electrical conductors, especially at elevated temperatures. This study encourages further research into defect chalcopyrites for applications in optoelectronics and thermoelectric energy conversion.

Low lattice thermal conductivity induced by interlayer anharmonicity in p-type BaFZnAs compound with high thermoelectric performance

Inspired by the excellent thermoelectric (TE) performance of ZrSiCuAs-type materials, the crystal structure, thermal and electronic transport mechanisms, and TE properties of the BaFZnAs compound are explored using first-principles calculations and Boltzmann transport theory. The BaFZnAs compound is an anisotropic material, with a direct bandgap of 1.20 eV determined by the Heyd-Scuseria-Ernzerhof (HSE06) functional. The [Zn2As2]2- layer within BaFZnAs compound forms carrier transport channel, which is beneficial for high power factor. The strong out-of-plane interlayer anharmonicity of the [Ba2F2]2+ and [Zn2As2]2- layers with weak interactions leads to a low lattice thermal conductivity (1.64 W/mK at 300 K) for the BaFZnAs compound. Based on the carrier relaxation time evaluated in the consideration of multiple carrier scattering rates and electronic transport parameters, the optimal ZTs of 1.44 and 2.06 are achieved for n-type and p-type BaFZnAs compounds at 900 K, associating with the corresponding ZTs of 2.10 (0.72) and 2.64 (0.51) along the a-axis and c-axis directions. Our present work not only offers multifaceted insights into the thermal and electronic transport properties of BaFZnAs compound, but also provides a new inspiration for further TE exploration of ZrSiCuAs-type materials.

Marcus Theory and Long-Range Activationless Transport in Molecular Junctions.

Intrachain transport in molecular junctions (MJs) longer than 5 nm has been modeled within the theoretical framework of Marcus theory. We show that in oligo(bisthienylbenzene)-based MJs, electronic transport involves polarons, localized on three monomers that are close to 4 nm in length. They hop and tunnel between adjacent localized sites with reorganization energies λ close to 400-600 meV and electronic coupling parameters Hab close to λ/2. As a consequence, the activation energy for intrachain transport, given by the equation ΔG* = (λ/4)(1 - 2Hab/λ)2, is close to zero, and transport along the chain is activationless, in agreement with experimental observation. On the contrary, similar calculations on conjugated oligonaphthalenefluoreneimine wires show that Hab is much less than λ/2 and predict that the activation energies for intrachain hopping between adjacent sites, close to λ/4, are ∼115 meV. This work proposes a new perspective for understanding long-range activationless transport in MJs beyond the tunneling regime.

Photo-induced collective charge-density-wave dynamics in bulk 1T-VSe2

We investigated temperature (T) and excitation density dependent ultrafast near-infrared (NIR) transient reflectivity dynamics in the charge density wave (CDW) phases of bulk layered 1T-VSe2 using NIR and visible excitations. The data reveal fingerprints of conventional non-adiabatic CDW collective dynamics with rather fast electronic order parameter dynamics showing sub-picosecond suppression and recovery. The slower T-dependent 100-ps dynamics indicates rather isotropic heat transport dominated by the lattice degrees of freedom.

Synthesis, structure elucidation, antioxidant properties, and theoretical calculations of new Schiff bases–isatin derivatives

Isatin-derived Schiff bases are the subject of many studies, finding wide application areas in polymer technology, pharmaceutical industry, and medicine. In this study, a series of new Schiff bases were prepared from monothiocarbohydrazones based on isatins with different substituents (5-F, 5-Br, 5-I, and 5-MeO). The chemical structures of the synthesized compounds were determined using 1H NMR, 13C NMR, FTIR spectroscopic techniques, and elemental analysis. Antioxidant activity determinations of 23 compounds were performed using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical quenching method. The highest percent inhibition value at 10 µM concentration was shown by compound number 22, 5-bromoisatin Schiff base containing 3-methoxy-4-hydroxy group. Compound 17, a 5-iodoisatin Schiff base containing 3-methoxy-4-hydroxy group, showed the highest antioxidant activity with an IC50 value of 9.76 ± 0.03 µM. In addition to the theoretical analysis of the compounds, both their spectroscopic and antioxidant properties were investigated. The ground-state geometries and some chemical reactivity parameters of the compounds were calculated using the B3LYP/6-311 + + G(2d,2p) approach. Besides intramolecular interactions, substituent effects, and some QTAIM parameters, the calculations were also performed to study the electronic properties of reactive N/O–H bonds and were used to interpret the experimental results. The effects of the electronic parameters and intramolecular interactions of reactive N/O–H bonds on the antioxidant properties of the compounds were investigated. Additionally, the relationships of DPPH reactions with delocalization indices of N/O-H bonds and the pattern of SET/HAT mechanisms with electronic variables were analyzed. Examination of electron and hydrogen atom transfer mechanisms has shown the dominance of electron transfer, supported by the correlation coefficients between IC50 values and SET reaction energies.

Measurement insights and error analysis of electronic parameters for ultrasonic transducers

Abstract Piezoelectric ultrasonic transducers with the function of energy conversation, as well as their numerous advantages in high-power density, quick response, flexible design, and service reliability, are involved in wide applications of industrial processing, precision driving, smart sensing, and medical services. The electromechanical equivalent circuit and Kirchhoff’s law indicate that mechatronics parameters are essential for performance evaluation, reliability analysis, and fault diagnosis of ultrasonic transducers. Importantly, the ultrasonic transducer is a time-variant system, data of one single parameter collected from a certain test cannot match with the data of another single parameter acquired from a different test. So, a synchronous and precise online measurement of electronic parameters is encouraged for performance evaluation and optimization design of ultrasonic transducers. With the combination of virtual instrument technology, an asynchronous measurement system of electrical excitation parameters for the ultrasonic transducers of linear driving motors was established in this study. Furthermore, the systematic measurement methods and error theory were illustrated, including the calculation methods and measuring circuits of electric signals. Experimental results proved that the proposed system and methods for measuring the input electronic power of ultrasonic transducer (e.g. effective value method for voltage and current, energy moment method for frequency, and spectrum analysis method for phase difference) are highly precise, quickly responsive, robust, and reliable for ultrasonic transducers. The findings of this study provide valuable references and suggestions for efficient, accurate, and online performance evaluation of ultrasonic transducers, particularly for piezoelectric transducers utilizing ultrasonic high-voltage exciting signals.

A voting-based ensemble classifier to predict phases and crystal structures of high entropy alloys through thermodynamic, electronic, and configurational parameters

This study aims to predict the various phases present in high entropy alloys (HEAs) and consequently classify their crystal structure employing multiple machine learning (ML) algorithms utilizing five thermodynamic, electronic and configurational parameters which are considered to be essential for the formation of HEA phases. The properties of a high entropy alloy can eventually be traced through accurate phase and crystal structure prediction, which is essential for selecting the ideal elements for designs. Twelve distinct ML algorithms were executed to predict the phases of HEAs, adopting an experimental database of 322 different HEAs, involving 33 amorphous (AM), 31 intermetallics (IM), and 258 solid solutions (SS) phases. Among the twelve ML models, Cat Boost Classifier displayed the optimum accuracy of 98.06 % for phase predictions. Further, crystal structure classification of the SS phase (body-centered cubic- BCC, face-centered cubic- FCC, and mixed body-centered and face-centered cubic- BCC+FCC) has endeavoured for better microstructure evolution using a different database containing of 194 additional HEAs data with 61 FCC, 76 BCC, and 57 BCC+FCC crystal structures and in comparison to the other models tested, the Gradient Boosting Classifier evolved with the highest accuracy of 86.90 %. An ensemble classifier was also introduced to improve the performance of the ML models, resulting in an accuracy increase to 98.70 % and 86.95 % for phase and crystal structure predictions, respectively. Additionally, the influence of parameters on model accuracy was determined independently.

First-principles calculation of structural, electronic, optical and thermoelectric properties of Li3TrAs2 (Tr = Al, Ga)

Computational analysis of the materials Li3TrAs2 (Tr = Al, Ga) through first principles DFT approach using WIEN2k code was done to evaluate the feasibility of the materials for several applications. The study comprises structural, electronic, optical and thermoelectric parameters. Structural parameters for the orthorhombic compounds with c/a variation in accordance to ground state energy is in well agreement with experimental data. From the electronic properties, direct bandgap semiconducting behavior of both compounds has been observed. Optical studies such as absorption coefficient and its direct bandgap nature implying the materials capability in utilizing in optoelectronic devices. Higher figure of merit (ZT) at ambient conditions implies the material to be good contender in thermoelectric devices such as waste heat recovery systems at room temperature. Based on the exciton binding energy from excitonic study reveals the weak or Mott-Wannier type exciton within both the material.

Electron acceleration and transport in the 2023-03-06 solar flare

We investigated in detail the M5.8 class solar flare that occurred on 2023-03-06. This flare was one of the first strong flares observed by the Siberian Radioheliograph in the microwave range and the Advanced Space-based Solar Observatory in the X-ray range. The flare consisted of two separate flaring events (a “thermal” and a “cooler” ones), and was associated with (and probably triggered by) a filament eruption. During the first part of the flare, the microwave emission was produced in an arcade of relatively short and low flaring loops. During the second part of the flare, the microwave emission was produced by energetic electrons trapped near the top of a large-scale flaring loop; the evolution of the trapped electrons was mostly affected by the Coulomb collisions. Using the available observations and the GX Simulator tool, we created a 3D model of the flare, and estimated the parameters of the energetic electrons in it.

Coumarin containing hetero[5/6]helical donor–acceptor molecules: Synthesis, photophysical properties and DFT studies

Coumarin containing hetero[5/6]helical derivatives with alkoxy substituent on coumarin ring were designed, synthesized and studied for their photophysical properties. Along with type of extended helical core around coumarin moiety, substitution on pendent aryl ring was also found to have significant effect on photophysical properties. Hetero [5]helical coumarin with furan ring in helical core and cyano substituted pendant aryl ring, compound 20a exhibited good quantum yield with blue fluorescence in both solid and solution state as compared to corresponding nitro analogue. For nitro substituted pendant aryl ring, phenanthrene moiety in helical core in compound 15b was found to play key role to show yellow fluorescence in hetero[6]helical coumarin. All the compounds were studied by DFT calculations for various structural as well as electronic parameters. TD-DFT calculations were studied for all the compounds to calculate various electronic parameters associated with excited state and correlated with the observed photophysical properties.

KCl-UCl3 molten salts investigated by Ab Initio Molecular Dynamics (AIMD) simulations: A comparative study with three dispersion models

Ab Initio Molecular Dynamics (AIMD) simulations are performed on molten KCl-UCl3 salt mixtures to determine energies, heat capacities, and densities. The density-dependent energy correction (DFT-dDsC), Grimme et al.'s DFT-D3, and Langreth & Lundqvist (vdW-cx) models are used for dispersion forces and combined with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation potential with a Hubbard U parameter for the 5f electrons of uranium. After validating predictions for the end-member systems to literature data, KCl-UCl3 mixtures are studied at select temperatures. Densities and energies both deviate from ideal solution behavior, with the maximum deviation occurring around 36% UCl3 for mixing energies and slightly lower (29% UCl3) for densities. Compared to the NaCl-UCl3 system, which was previously investigated using the same simulation methodologies, the KCl-UCl3 density and mixing energy deviations from ideal solution behavior are larger by almost a factor of two. No deviation from ideal solution behavior for heat capacity was observed. The AIMD predictions for mixing energies and densities agree qualitatively with experimental data, though the spread in data obtained from the various dispersion force models utilized, measurements, and empirical estimates makes strong conclusions difficult. The dependence of thermodynamic and thermophysical properties on composition is correlated with the local chemistry of the solution phase, in particular, the tendency of UCl3 to form network structures.

Coumarin Schiff base derivatives with terminal cyano group: Synthesis, Mesomorphic properties and DFT investigation

Coumarin Schiff base derivatives with terminal cyano group were synthesized and analysed for their mesomorphic behaviour. The homologous series CN6–16 (n = 6,8,10,12,14,14,16) with 4-cyano benzaldehyde, lower member (n = 6,8) exhibited enantiotropic nematic mesophase, while smectic A mesophase started appearing with n = 8 during cooling process. Enantiotropic smectic A mesophase was observed with higher chain length n = 10,12,14,16. Similar trend of mesomorphic properties was exhibited by Schiff base derivatives BPCN8–14. Introduction of cyano biphenyl at aldehyde end of the molecule has led to formation of stable smectic A mesophase as compared to that by compounds CN8–14. Introduction of ester linkage in Schiff based derivatives, compounds ECN10–12 and RECN10–12 showed smectic A mesophase with high clearing temperature. VT-XRD analysis of two compounds has confirmed orthogonal smectic A mesophase. Additionally, DFT calculations were carried out for all the newly synthesized compounds and compared with similar literature molecules for various structural and electronic parameters followed by their correlation with the mesophase type and stability.

PM3 QUANTUM CHEMICAL CALCULATIONS OF THE BIOACTIVE ALA-TYR DIPEPTIDE

Ala-Tyr (Alanine-Tyrosine) dipeptide is a compound with hypertensive and high antioxidant effect. Here, the structural features of this molecule were studied using the PM3 semi-empirical quantum-chemical method. In order to investigate the research, the initial coordinates of the molecule were obtained by the molecular mechanics method. Geometric and electronic parameters, HOMO and LUMO energies, energy gap, dipole moment and partial charges of atoms were calculated for the stable conformations, belonging to both folded and extended shapes of the dipeptide backbone. The obtained results can be used in the research of the structure-function relationships of the investigated bioactive dipeptide and in the design of new peptidomimetics.

Quantification of the Donor-Acceptor Character of Ligands by the Effective Fragment Orbitals.

Metal-ligand interactions are at the heart of transition metal complexes. The Dewar-Chat-Duncanson model is often invoked, whereby the metal-ligand bonding is decomposed into the simultaneous ligand→metal electron donation and the metal→ligand back-donation. The separate quantification of both effects is not a trivial task, neither from experimental nor computational exercises. In this work we present the effective fragment orbitals (EFOs) and their occupations as a general procedure beyond the Kohn-Sham density functional theory (KS-DFT) framework for the identification and quantification of donor-acceptor interactions, using solely the wavefunction of the complex. Using a common Fe(II) octahedral complex framework, we quantify the σ-donor, π-donor, and π-acceptor character for a large and chemically diverse set of ligands, by introducing the respective descriptors σd, πd, and πa. We also explore the effect of the metal size, coordination number, and spin state on the donor/acceptor features. The spin-state is shown to be the most critical effect, inducing a systematic decrease of the sigma donation and π-backdonation going from low spin to high spin. Finally, we illustrate the ability of the EFOs to rationalize the Tolman electronic parameter and the trans influence in planar square complexes in terms of these new descriptors.

Ultrafast excitonic dynamics in DNA: Bridging correlated quantum dynamics and sequence dependence.

After photoexcitation of DNA, the excited electron (in the LUMO) and the remaining hole (in the HOMO) localized on the same DNA base form a bound pair, called the Frenkel exciton, due to their mutual Coulomb interaction. In this study, we demonstrate that a tight-binding (TB) approach, using TB parameters for electrons and holes available in the literature, allows us to correlate relaxation properties, average charge separation, and dipole moments to a large ensemble of double-stranded DNA sequences (all 16384 possible sequences with 14 nucleobases). This way, we are able to identify a relatively small subensemble of sequences responsible for long-lived excited states, high average charge separation, and high dipole moment. Further analysis shows that these sequences are particularly T rich. By systematically screening the impact of electron-hole interaction (Coulomb forces), we verify that these correlations are relatively robust against finite-size variations of the interaction parameter, not directly accessible experimentally. This methodology combines simulation methods from quantum physics and physical chemistry with statistical analysis known from genetics and epigenetics, thus representing a powerful bridge to combine information from both fields.

Formation of amygdalin/β-cyclodextrin derivatives inclusion complexes for anticancer activity assessment in human cervical carcinoma HeLa cell line

Nanoencapsulation has gained considerable attention because of its unique features and advantages in anticancer drug delivery. Amygdalin (AMY) is an anticancer compound, showing limitations in its applications by low stability. Herein, the inclusion complexes (ICs) of AMY with β-cyclodextrin (βCD), and its derivatives such as 2-hydroxypropyl-βCD (HPβCD) and methyl-βCD (MβCD) were fabricated. The fabricated AMY/CD-ICs were thoroughly evaluated using Fourier-transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric/differential thermal analysis, proton nuclear magnetic resonance, ultraviolet–visible diffuse reflectance spectroscopy, and photoluminescence techniques. Double reciprocal profile study of the absorption and fluorescence spectra revealed that the AMY formed the ICs with βCD derivatives at a guest/host stoichiometric ratio of 1/1. The thermal stability of AMY was enhanced as the IC formation aid observed by the shift of thermal degradation temperature of AMY from the range of ∼ 220–250 °C to > 295 °C. Theoretical analyses of the energetic, electronic, and global reactivity parameters of the AMY/CD-ICs were evaluated using the PM3 method. Further assessment of the dissolution diagrams of AMY/CD-ICs revealed a burst release profile. In addition, cell toxicity was evaluated using the MTT assay, and the results showed that AMY/CD-ICs had significantly more efficacious in inhibiting HeLa cancer cells than AMY. These results proved that the IC formations with CDs significantly enhanced the anticancer activity of AMY.

Investigation of GeSe Photovoltaic Device Performance via 1-Dimensional Computational Modelling

Germanium selenide (GeSe) is a potential absorber material for thin film solar cells. However, many physical, electronic parameters and practical defect configurations that result in different effects on the performance of GeSe solar cells are not fully understood. In this study, a baseline of a GeSe thin film solar cell was designed and simulated using SCAPS-1D simulator. The physical and electronic parameters of the absorber layer is varied to investigate their effect on the performance of the solar cell. The simulation uses absorption files extracted from Xue et al. 2016 and the SCAPS-1D absorption model. Practical defect configurations are also introduced in GeSe thin film solar cells to optimize solar cell performance. Simulation results show that baseline GeSe solar cells had obtained Voc 0.62 V, Jsc 39.52 mA/cm<sup>2</sup>, FF 79.34 and ƞ 19.48%. Simulation using the SCAPS-1D absorption model achieved a more accurate JSC contour graph compared to simulation using absorption files extracted from Xue et al. 2016. The highest efficiency of 26.13% was achieved at 1.40 eV bandgap, 4.27 eV electron affinity, 10 cm2/Vs hole mobility, 1E+18 1/cm<sup>3</sup> hole concentration and 2000 nm GeSe layer thickness. For bulk defect, an increase in defect concentrations or capture cross section hole and electron (σ) reduce efficiency. For interfacial defect GeSe/CdS, total density of 1E+12 1/cm<sup>2</sup> with σ of 1E-13 cm<sup>2</sup>, total density of 1E+18 1/cm2 with σ of 1E-19 cm<sup>2</sup>, total density of 1E+16 1/cm<sup>2</sup> and 1E+18 1/cm<sup>2</sup> with σ of 1E-16 cm<sup>2</sup> have critical impact to solar cell.

Bifurcation analysis of electron-acoustic waves in electron beam-plasma with suprathermal electrons

It has investigated the properties of nonlinear electron-acoustic waves propagating in a four-component collisionless, unmagnetized plasma. The system consists of cool inertial background electrons of temperature T c , the cool inertial electron beam of temperature T b , hot inertialess suprathermal electrons modeled by a κ-distribution of temperature T h , and ions. The nonlinear modified Korteweg-de Vries-Burgers (mKdV-Burgers) equation that characterizes the electron acoustic waves in such a plasma model is derived. The wave solutions of the resultant mKdV-Burgers equation are investigated using planar dynamical system bifurcation theory. The unperturbed hot, cool, and beam electron densities and the superthermal electron parameter are revealed to have a considerable influence on the nonlinear electron-acoustic traveling waves and the associated electric fields. The system evolves also monotonic shock waves when the dissipation term dominates over the dispersion term. The current model might be useful for understanding the generation of nonlinear electron-acoustic waves in a variety of astrophysical plasma settings, including the Earth's magnetosphere.