Electronic Spectra Research Articles

Synthesis and Spectral Analysis of Chromium, Copper Complexes of 2-Hydroxy-1, 2-diphenylethan-1

Various chemical process have been utilized to analyze chromium (II) and copper (II) complexes with Benzoin. The fore mentioned complexes were analyzed for elemental analyses, and characterized by infrared, electronic spectra, NMR spectroscopy. The data analysis showed the metal ion formation of 1:1 ligand to metal ratio representing the [Cr (B)] H2O and [Cu (B)] 2H2O ionic complex in which B represents the Benzoin. According to the data analyzed by Infrared spectroscopy, it is through the carbonyl and hydroxyl oxygen’s of the Benzoin that chelation chemistry takes place. The complex structural analysis was elucidated by electronic spectral data analysis and by proton NMR spectroscopy. The complex systems with the metals also showed antimicrobial property against many bacterial strains.

Electronic structure and composition of tin oxide thin epitaxial and magnetron layers according to synchrotron XANES studies

The materials of the tin-oxygen system and thin-film structures based on them are modern and actual for the creation of a wide range of electronic devices, for example, resistive gas sensors of high sensitivity and short response time with low energy consumption and high manufacturability. An important direction in the study of such materials and structures is the control of properties with variations in technological formation regimes. Information on the composition, local atomic and electronic structure of thin layers of the tin-oxygen system with varying approaches to their production is in demand. The work is devoted to the study of the electronic structure of thin layers of tin oxides obtained by modern methods of molecular beam epitaxy and magnetron sputtering. A study of the local partial density of electronic states in the conduction band by X-ray absorption near edge structure spectroscopy of tin and oxygen has been carried out. The data were obtained using high-intensity synchrotron radiation, which allows varying the monochromatized radiation quantum energy without loss in intensity, that is necessary to obtain high-resolution X-ray spectral data. It is shown that the composition, local atomic surrounding, electronic spectrum and their features depend on the technology of formation and storage conditions of the studied structures. Synchrotron X-ray spectroscopy data show the presence of intermediate oxides of the tin-oxygen system in the studied materials after prolonged storage in laboratory conditions. The data obtained indicate the possibility of controlled variation in the composition, local atomic surrounding and electronic spectrum of thin-film structures of tin oxides of small thickness. The results of the work can be used in the formation and subsequent modification of thin and ultrathin layers of tin oxides by magnetron sputtering and molecular beam epitaxy, as well as in their further application as active layers of microelectronics devices

Di- and Tricyanovinyl-Substituted Triphenylamines: Structural and Computational Studies.

We report herein on the solid-state structures of three closely related triphenylamine derivatives endowed with tricyanovinyl (TCV) and dicyanovinyl (DCV) groups. The molecules described contain structural features commonly found in the design of functional organic materials, especially donor-acceptor molecular and polymeric architectures. The common feature noticeable in these structures is the impact of these exceptionally strong electron-accepting groups in forcing partial planarity of the portion of the molecule carrying these groups and directing the molecular packing in the solid state, resulting in the formation of π-stacks of dimers within the unit cell of each. Stacks are formed between phenyl groups bearing electron-accepting groups on two adjacent molecules. Short π-π stack distances ranging from 3.283 to 3.671 Å were observed. Such motif patterns are thought to be conducive for better charge transport in organic semiconductors and enhanced device performance. Intramolecular charge transfer is evident from the shortening of the observed experimental bond lengths in all three compounds. The nitrogen atoms (of the cyano groups) have been shown to be extensively involved in short contacts in all three structures, primarily through C-H···NC interactions with distances as short as 2.462 Å. The compounds reported here are (3,3-dicyano-2-(4-(diphenylamino)phenyl)-1λ3-allylidene)amide or tricyanovinyltriphenylamine, Ph3NTCV (1); 2-(4-(diphenylamino)benzylidene)-malononitrile or dicyanovinyltriphenylamine, Ph3NDCV (2); and (3,3-dicyano-2-(4-(di-p-tolylamino)phenyl)-1λ3-allylidene)amide or dimethyltricyanovinyltriphenylamine, Me2Ph3NTCV (3). Results of density functional theory calculations using DFT-B3LYP/6-31G(d,p) indicate the lowering of LUMO levels as a result of the introduction of these groups with band gaps of 3.13, 2.61, and 2.55 eV for compounds 1-3, respectively, compared with 4.65 eV calculated for triphenylamine. This is supported by the electronic and fluorescence spectra of these molecules with absorption λmax of 483, 515, and 545 nm for compounds 1, 2, and 3, respectively.

Ionic strength and phase systems influence nanotubular material functionality

We synthesized novel thiacyanine chromonic liquid crystals (CLCs) and structurally characterized using NMR and mass spectrometry. The impact of distinct substitution at the para position of aromatic counter anions, aliphatic counter ion chain length, and varied spacer parity of thiacyanine dyes on CLC formation is investigated. Liquid crystal properties of the synthesized dyes are characterized by polarizing optical microscopy (POM) and X-ray diffraction (XRD) studies. Dyes exhibit nematic (N), lamellar (Lα), columnar rectangular (Colr), and columnar oblique (Colob) CLCs at different concentrations in the water. Electronic absorption spectra reveal Scheibe aggregation in all the dyes. Cylicvoltametry studies confirm redox behaviour in TC-1a and TC-5e dyes. Chromonic LCs hybrid nano-materials are synthesized using sol–gel method. Scanning electron microscopy employed to confirm nano tubular fiber structure of the hybrid nanomaterilals..

The application of C/Sb composite multilayer films on fast flexible phase change memory

In this paper, the phase transformation properties of C/Sb composite multilayer films based on flexible substrates were studied. After different times of bending, the flexible films can still achieve amorphous to crystalline phase transition, but the crystalline resistance increases to different degrees. When the bending times are less than 15000 times, the deformation makes the grain fine, the surface of the film tends to be flat, the surface electric field effect is weakened, and the resistance drift is reduced. When the bending times are higher than 15000 times, cracks begin to appear in the film, and the cracks’ depth and width increase with the bending times. The distribution of C and Sb elements at the crack was analyzed by scanning electronic microscope energy spectrum. The phase change memory device of C/Sb composite multilayer film based on flexible PEEK substrate has been made, and the rapid reversible resistance transition (∼10 ns) in various complex states has been successfully achieved. This research provides a new idea for flexible information storage.

Electric Field Susceptibility of Chlorophyll c Leads to Unexpected Excitation Dynamics in the Major Light-Harvesting Complex of Diatoms.

Diatoms are one of the most abundant photosynthetic organisms on earth and contribute largely to atmospheric oxygen production. They contain fucoxanthin and chlorophyll-a/c binding proteins (FCPs) as light-harvesting complexes with a remarkable adaptation to the fluctuating light on ocean surfaces. To understand the basis of the photosynthetic process in diatoms, the excitation energy funneling within FCPs must be probed. A state-of-the-art multiscale analysis within a quantum mechanics/molecular mechanics framework has been employed. To this end, the chlorophyll (Chl) excitation energies within the FCP complex from the diatom Phaeodactylum tricornutum have been determined. The Chl-c excitation energies were found to be 5-fold more susceptible to electric fields than those of Chl-a pigments and thus are significantly lower in FCP than in organic solvents. This finding challenges the general belief that the excitation energy of Chl-c is always higher than that of Chl-a in FCP proteins and reveals that Chl-c molecules are much more sensitive to electric fields within protein scaffolds than in Chl-a pigments. The analysis of the linear absorption spectrum and the two-dimensional electronic spectra of the FCP complex strongly supports these findings and allows us to study the excitation transfer within the FCP complex.

Glutathione detection in water and milk using a new probe DCYP based on benzopyranonitrile

Glutathione (GSH) is a potent antioxidant, fragrance, and anti-browning agent in the field of food chemistry. The accurate GSH evaluation in food and vegetables is critical for instructing the right supplementation of GSH in body. However, most reported GSH fluorescent probes were utilized for the biological imaging. In this study, a new probe DCYP-GSH was developed by coupling of benzopyranonitrile as signal reporter to N-methylpyridine through C = C bond as binding site. Notably, a significant increase in fluorescence intensity and a λmax red-shift of DCYP-GSH in electron spectra were found as a result of the response to GSH. Quantitative detection of GSH in water and milk samples were achieved using probe DCYP-GSH. The development of DCYP-GSH was anticipated to provide an effective toolkit for food safe evaluation.

Beam quality and the mystery behind the lower percentage depth dose in grid radiation therapy

Grid therapy recently has been picking momentum due to favorable outcomes in bulky tumors. This is being termed as Spatially Fractionated Radiation Therapy (SFRT) and lattice therapy. SFRT can be performed with specially designed blocks made with brass or cerrobend with repeated holes or using multi-leaf collimators where dosimetry is uncertain. The dosimetric challenge in grid therapy is the mystery behind the lower percentage depth dose (PDD) in grid fields. The knowledge about the beam quality, indexed by TPR20/10 (Tissue Phantom Ratio), is also necessary for absolute dosimetry of grid fields. Since the grid may change the quality of the primary photons, a new kq,q0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\mathbf{k}}_{\\mathbf{q},{\\mathbf{q}}_{0}}$$\\end{document} should be evaluated for absolute dosimetry of grid fields. A Monte Carlo (MC) approach is provided to resolving the dosimetric issues. Using 6 MV beam from a linear accelerator, MC simulation was performed using MCNPX code. Additionally, a commercial grid therapy device was used to simulate the grid fields. Beam parameters were validated with MC model for output factor, depth of maximum dose, PDDs, dose profiles, and TPR20/10. The electron and photon spectra were also compared between open and grid fields. The dmax is the same for open and grid fields. The PDD with grid is lower (~ 10%) than the open field. The difference in TPR20/10 of open and grid fields is observable (~ 5%). Accordingly, TPR20/10 is still a good index for the beam quality in grid fields and consequently choose the correct kq,q0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\mathbf{k}}_{\\mathbf{q},{\\mathbf{q}}_{0}}$$\\end{document} in measurements. The output factors for grid fields are 0.2 lower compared to open fields. The lower depth dose with grid therapy is due to lower depth fluence with scatter radiation but it does not impact the dosimetry as the calibration parameters are insensitive to the effective beam energies. Thus, standard dosimetry in open beam based on international protocol could be used.

Solvation model, Vibrational analysis, Electronic level, Non-Covalent interactions and Molecular docking investigations of 6-Chloro-2-(4-Aminophenyl)-1H-Benzimidazole

6-Chloro-2-(4-Aminophenyl)-1H-Benzimidazole compound were synthesized and characterized by SC-XRD, FT-IR, FT-Raman, UV–Vis, 1H NMR, and 13C NMR and analyzed with experimental data. The DFT approach with the B3LYP functional and 6-311++G(d,p) basis set was used to calculate the geometry parameters and wavenumbers of the title compound. Electronic absorption spectra and 1H–13C NMR studies have been computed in gas and solvents (dimethylsulfoxide, chloroform, and H2O) by using the TD-DFT and the IEFPCM solvation model. The HOMO-LUMO energy band gap has also been determined. To identify the electron localization density and weak interactions, the Multiwin-3.8 was subjected to a topological analysis and non-covalent interactions, including ELF, LOL, DORI and ED.Studies of donor–acceptor connections were performed using NBO analysis. To calculate contributions to the molecular orbitals, TDOS was determined. Molecular electrostatic potential (MEP) reveals the chemical reactivity sites for the reaction. The antibacterial activity of the compound has been assessed with a zone of inhibition by the well diffusion method using a panel of selected gram-positive Staphylococcus aureus (MTCC-3160), Enterococcus faecalis (MTCC-3159) and gram-negative Pseudomonas aeruginosa (MTCC-4030), Escherichia coli (MTCC-1667) bacterial strains that have shown better activity than the standard drug (Ciprofloxacin). Finally, molecular docking and pharmacokinetics have been agreed upon to understand the binding energy of the ligand–protein interaction.

Inter-subunit energy transfer processes in a minimal plant photosystem II supercomplex.

Photosystem II (PSII) is an integral part of the photosynthesis machinery, in which several light-harvesting complexes rely on inter-complex excitonic energy transfer (EET) processes to channel energy to the reaction center. In this paper, we report on a direct observation of the inter-complex EET in a minimal PSII supercomplex from plants, containing the trimeric light-harvesting complex II (LHCII), the monomeric light-harvesting complex CP26, and the monomeric PSII core complex. Using two-dimensional (2D) electronic spectroscopy, we measure an inter-complex EET timescale of 50 picoseconds for excitations from the LHCII-CP26 peripheral antenna to the PSII core. The 2D electronic spectra also reveal that the transfer timescale is nearly constant over the pump spectrum of 600 to 700 nanometers. Structure-based calculations reveal the contribution of each antenna complex to the measured inter-complex EET time. These results provide a step in elucidating the full inter-complex energy transfer network of the PSII machinery.

Artificial-Intelligence-Enhanced On-the-Fly Simulation of Nonlinear Time-Resolved Spectra.

Time-resolved spectroscopy is an important tool for unraveling the minute details of structural changes in molecules of biological and technological significance. The nonlinear femtosecond signals detected for such systems must be interpreted, but it is a challenging task for which theoretical simulations are often indispensable. Accurate simulations of transient absorption or two-dimensional electronic spectra are, however, computationally very expensive, prohibiting the wider adoption of existing first-principles methods. Here, we report an artificial-intelligence-enhanced protocol to drastically reduce the computational cost of simulating nonlinear time-resolved electronic spectra, which makes such simulations affordable for polyatomic molecules of increasing size. The protocol is based on the doorway-window approach for the on-the-fly surface-hopping simulations. We show its applicability for the prototypical molecule of pyrazine for which it produces spectra with high precision with respect to ab initio reference while cutting the computational cost by at least 95% compared to pure first-principles simulations.

Design, synthesis, characterization, in vitro cytotoxic, antimicrobial, antioxidant studies, DFT, thermal and molecular docking evaluation of biocompatible Co(II) complexes of N4O4-macrocyclic ligands

Bioactive cobalt (II) macrocyclic complexes [Co(N4O4ML1)Cl2]-[Co(N4O4ML3)Cl2] have been synthesized by using the macrocyclic ligands [N4O4ML1], [N4O4ML2], and [N4O4ML3] that have an N4O4 core. These three macrocyclic ligands were all isolated in pure form, together with their complexes. Microanalytical investigations, FT-IR NMR, Mass, magnetic moments, electronic, PXRD, TGA, and EPR spectrum studies were used to analyse their structures. For these complexes, an octahedral geometry is proposed for the metal ion. By using molecular weights and conductivity measurements the monomeric and non-electrolytic nature has been confirmed. The Coats-Redfern and FWO methods are used to determine the thermodynamic characteristics of the ligands and their Co(II) complexes. The molecular modelling using the DFT technique displays the bond angle, bond lengths and quantum chemical properties. To determine their ability to prevent the growth of harmful fungus and bacteria, the ligands [N4O4ML1]- [N4O4ML3] and their complexes were tested in vitro against A. Niger, C. albicans and B. subtilis, S. aureus, E. coli and S. typhi fungal and bacterial organisms, respectively. By using DPPH free radical scavenger assays, the in vitro antioxidant capabilities of each compound were evaluated. The [Co(N4O4ML3)Cl2] antioxidative capabilities revealed significant radical scavenging power. The MTT assay was used to assess the toxicity of all the synthesised compounds under inquiry on MCF-7, HeLa, and A549 cancer cells. The findings revealed that the ligand and the compounds gave outstanding IC50 values in the range of 9.07–36.25 (uM) at a concentration of 25 ppm. Among all the substances evaluated, [Co(N4O4ML3)Cl2] complex was discovered to be the most active and least cytotoxic. Additionally, docking investigations of the produced compounds were carried out in order to validate the biological outcomes.

Finite-temperature vibronic spectra from the split-operator coherence thermofield dynamics.

We present a numerically exact approach for evaluating vibrationally resolved electronic spectra at finite temperatures using the coherence thermofield dynamics. In this method, which avoids implementing an algorithm for solving the von Neumann equation for coherence, the thermal vibrational ensemble is first mapped to a pure-state wavepacket in an augmented space, and this wavepacket is then propagated by solving the standard, zero-temperature Schrödinger equation with the split-operator Fourier method. We show that the finite-temperature spectra obtained with the coherence thermofield dynamics in a Morse potential agree exactly with those computed by Boltzmann-averaging the spectra of individual vibrational levels. Because the split-operator thermofield dynamics on a full tensor-product grid is restricted to low-dimensional systems, we briefly discuss how the accessible dimensionality can be increased by various techniques developed for the zero-temperature split-operator Fourier method.

Synthesis, crystal structure and computational studies of water and pyrazine-bound magnesium 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin

The synthesis and characterization of two magnesium porphyrins [Mg(TDMPP)(H2O)2], 1 and [Mg(TDMPP)(pyz)2], 2 where TDMPP = 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin and pyz = pyrazine have been described. The compound 1 in the presence of pyrazine forms hexa-coordinated compound [Mg(TDMPP)(pyz)2], 2. Both compounds were structurally characterized. Theoretical calculations like structure optimization, calculation of energy of molecular orbitals and simulation of electronic spectra were performed. The HOMO-LUMO energy difference in compound 2 (2.53 eV) is slightly lower than in compound 1 (2.56 eV) which supports the redshift of UV–Vis peaks on binding pyrazine to compound 1.

Synthesis and Characterization of Isostructural Th(IV) and U(IV) Pyridine Dipyrrolide Complexes.

A series of pyridine dipyrrolide actinide(IV) complexes, (MesPDPPh)AnCl2(THF) and An(MesPDPPh)2 (An = U, Th, where (MesPDPPh) is the doubly deprotonated form of 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine), have been prepared. Characterization of all four complexes has been performed through a combination of solid- and solution-state methods, including elemental analysis, single crystal X-ray diffraction, and electronic absorption and nuclear magnetic resonance spectroscopies. Collectively, these data confirm the formation of the mono- and bis-ligated species. Time-dependent density functional theory has been performed on all four An(IV) complexes, providing insight into the nature of electronic transitions that are observed in the electronic absorption spectra of these compounds. Room temperature, solution-state luminescence of the actinide complexes is presented. Both Th(IV) derivatives exhibit strong photoluminescence; in contrast, the U(IV) species are nonemissive.

A DFT+U study of carbon nanotubes under influence of a gate voltage

A possibility of appearance of antiferromagnetic ordering in armchair carbon nanotubes and graphene is studied using density functional theory within a DFT+U approach. It is shown that the Coulomb repulsion between electrons in the π-orbitals of graphene would need to reach a threshold value of Uc=3.6eV, in order to stabilize the antiferromagnetic order and an energy gap in an electron spectrum at the Fermi level. In the carbon nanotubes the threshold value Uc for appearance of the antiferromagnetism decreases with the nanotube’s diameter. For an intermediate value of U<Uc the dependence of the energy gap on the diameter of nanotube is well described by a power law in agreement with earlier experimental findings.The antiferromagnetism in the carbon nanotubes is suppressed by departure of the Fermi level from a neutrality point. The latter result can qualitatively explain experimentally observed gate voltage dependence of the energy gap in junctions with the suspended carbon nanotubes as well as the absence of the energy gap in junctions with nanotubes deposited on some substrates.

Electronic and magnetic properties of ZnSeS solid solution modified by Mn impurity, Zn vacancy and pressure

The spin-polarized electronic energy spectra of the ZnSeS solid solution were obtained based on calculations for the supercell, which contains 64 atoms. At the first stage, the properties of the material based on the Mn:ZnSeS supercell, in which Mn replaces the Zn atom, were calculated. The calculation results reveal that the material is a semiconductor for both spin orientations. The second stage is based on the simultaneous presence of a Mn impurity and a cation vacancy. Comparing the results of the first two stages allows us to reveal significant changes in the electronic energy structure caused by the cation vacancy. The material with a vacancy exhibits metallic properties for both spin orientations. The third stage is implemented for the supercell without a vacancy, but under the action of hydrostatic pressure. The material exhibits semiconducting properties for both values of the spin moment. At the fourth stage, the Mn:ZnSeS supercell with a vacancy and under pressure is considered. In the presence of pressure and a VZn vacancy, the ZnMnSeS material exhibits metallic properties for both spin orientations. A material with a vacancy and under pressure can be characterized as a magnetic metal.

Acceleration characteristics of hot electrons resulted from magnetic reconnection process driven by double-beam intense laser pulses in near critical density plasmas

In this work, we investigated the magnetic annihilation and reconnection and the resulted hot electron acceleration driven by double-beam intense laser pulses in two-layer near critical density (NCD) plasma target. The results are obtained by performing two-dimensional (2D) particle-in-cell (PIC) simulations. It is found that a quasi-mono-energetic peak can be formed in the energy spectrum of electrons accelerated by the process of magnetic field annihilation (MA) at cutoff energy. Electron spectra feature depends on the length of the second low-density layer. This suggests that the process of relativistic magnetic annihilation may be controlled in experiments by target design.

Synthesis, characterization, PXRD studies, and theoretical calculation of the effect of gamma irradiation and antimicrobial studies on novel Pd(II), Cu(II), and Cu(I) complexes.

The main objective of this study is to synthesize and characterize of a new three complexes of Pd (II), Cu (II), and Cu (I) metal ions with novel ligand ((Z)-2-(phenylamino)-N'-(thiophen-2-ylmethylene)acetohydrazide) H2LB. The structural composition of new compounds was assessed using several analytical techniques including FT-IR, 1H-NMR, electronic spectra, powder X-ray diffraction, and thermal behavior analysis. The Gaussian09 program employed the Density Functional Theory (DFT) approach to optimize the geometry of all synthesized compounds, therefore obtaining the most favorable structures and crucial parameters. An investigation was conducted to examine the impact of γ-irradiation on ligands and complexes. Before and after γ-irradiation, the antimicrobial efficiency was investigated for the activity of ligands and their chelates. The Cu(I) complex demonstrated enhanced antibacterial activity after irradiation, as well as other standard medications such as ampicillin and gentamicin. Similarly, the Cu(I) complex exhibited superior activity against antifungal species relative to the standard drug Nystatin. The docking investigation utilized the target location of the topoisomerase enzyme (2xct) chain A.

Total absorption spectrum of benzene aggregates obtained from two different approaches.

The study of molecular aggregation effects on the electronic spectrum is essential for the development of optoelectronic devices. However, investigating the entire valence absorption spectrum of aggregates using quantum mechanical methods is a challenging task. In this work, we perform systematic simulations of the absorption spectrum of benzene molecular clusters up to 35 eV applying two approaches based on time-dependent density functional theory. The results show that depending on the dimer packing, different energy shifts occur for the symmetry allowed [Formula: see text] transition, in comparison to the monomer. The transition intensity increases for the band around 6 eV for larger aggregates from the monomer to dimers and tetramer, indicating the occurrence of the symmetry forbidden (in [Formula: see text] point group) [Formula: see text] [Formula: see text] transition. The benzene crystal exhibits a large redshift following the experimental spectrum. Also, the continuum regions of all spectra show a good agreement with the experiments both in gas and solid phases. Geometry optimization of the monomer was carried out with Gaussian 09 software using the PBE0/def2-TZVP level of theory. We used dimers and tetramer molecular geometries extracted from the experimental crystal structure. The absorption spectra were directly obtained by the Liouville-Lanczos TDDFT approach with plane waves basis set or indirectly by TDDFT pseudo-spectra calculated in a [Formula: see text] basis followed by analytic continuation procedure to obtain complex polarizability. The former is available at Quantum ESPRESSO, and the latter was calculated using Gaussian 09 with the post-processing performed with a code previously developed in our group.