Influence of degeneracy of energy levels on possibility of using the method of density functional in the case of low-dimensional systems

In the present research, B45H36N45 Born Nitride (9,9) nanotube (BNNT) and Al45H36N45 Aluminum nitride (9,9) nanotube (AlNNT) have been studied, both having the same length of 5 angstroms. The main reason for choosing boron nitride nanotubes is their interesting properties compared with carbon nanotubes. For example, resistance to oxidation at high temperatures, chemical and thermal stability higher rather than carbon nanotubes and conductivity in these nanotubes, unlike carbon nanotubes, does not depend on the type of nanotube chirality. The method used in this study is the density functional theory (DFT) at Becke3, Lee-Yang-Parr (B3LYP) method and 6-31G* basis set for all the calculations. At first, the samples were simulated and then the optimized structure was obtained using Gaussian 09 software. The structural parameters of each nanotube were determined in 5 layers. Frequency calculations in order to extract the thermodynamic parameters and natural bond orbital (NBO) calculations have been performed to evaluate the electron density and electrostatic environment of different layers, energy levels and related parameters, such as ionization energy and electronic energy, bond gap energy and the share of hybrid orbitals of different layers.

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Unraveling the electrochemical and spectroscopic properties of neutral and negatively charged perylene tetraethylesters

Scientific Reports ◽

10.1038/s41598-021-95551-0 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Christian Wiebeler ◽

Joachim Vollbrecht ◽

Adam Neuba ◽

Heinz-Siegfried Kitzerow ◽

Stefan Schumacher

Keyword(s):

Absorption Spectra ◽

Density Functional ◽

Energy Levels ◽

Spectroscopic Properties ◽

Absorption Bands ◽

Functional Theory ◽

Vertical Excitation ◽

Hartree Fock ◽

Tauc Plot ◽

Electrochemical Approach

AbstractA detailed investigation of the energy levels of perylene-3,4,9,10-tetracarboxylic tetraethylester as a representative compound for the whole family of perylene esters was performed. It was revealed via electrochemical measurements that one oxidation and two reductions take place. The bandgaps determined via the electrochemical approach are in good agreement with the optical bandgap obtained from the absorption spectra via a Tauc plot. In addition, absorption spectra in dependence of the electrochemical potential were the basis for extensive quantum-chemical calculations of the neutral, monoanionic, and dianionic molecules. For this purpose, calculations based on density functional theory were compared with post-Hartree–Fock methods and the CAM-B3LYP functional proved to be the most reliable choice for the calculation of absorption spectra. Furthermore, spectral features found experimentally could be reproduced with vibronic calculations and allowed to understand their origins. In particular, the two lowest energy absorption bands of the anion are not caused by absorption of two distinct electronic states, which might have been expected from vertical excitation calculations, but both states exhibit a strong vibronic progression resulting in contributions to both bands.

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A New Piano-Stool Ruthenium(II) P-Cymene-Based Complex: Crystallographic, Hirshfeld Surface, DFT, and Luminescent Studies

Crystals ◽

10.3390/cryst11010013 ◽

2020 ◽

Vol 11 (1) ◽

pp. 13

Author(s):

Mohd. Muddassir ◽

Abdullah Alarifi ◽

Mohd. Afzal

Keyword(s):

Density Functional ◽

Weak Interactions ◽

Energy Levels ◽

Hirshfeld Surface ◽

Binding Energies ◽

Orbital Energy ◽

Aminosalicylic Acid ◽

Full Characterization

A new complex (Ru(η6-p-cymene)(5-ASA)Cl2) (1) where 5-ASA is 5-aminosalicylic acid has been prepared by reacting the ruthenium arene precursors ((η6-arene)Ru(μ-Cl)Cl)2, with the 5-ASA ligands in a 1:1 ratio. Full characterization of complex 1 was accomplished by elemental analysis, IR, and TGA following the structure obtained from a single-crystal X-ray pattern. The structural analysis revealed that complex 1 shows a “piano-stool” geometry with Ru-C (2.160(5)- 2.208(5)Å), Ru-N (2.159(4) Å) distances, which is similar to equivalents sister complex. Density functional theory (DFT) was used to calculate the significant molecular orbital energy levels, binding energies, bond angles, bond lengths, and spectral data (FTIR, NMR, and UV–VIS) of complex 1, consistent with the experimental results. The IR and UV–VIS spectra of complex 1 were computed using all of the methods and choose the most appropriate way to discuss. Hirshfeld surface analysis was also executed to understand the role of weak interactions such as H⋯H, C⋯H, C-H⋯π, and vdW interactions, which play a significant role in the crystal environment’s stability. Moreover, the luminescence results at room temperature show that complex 1 gives a more intense emission band positioned at 465 nm upon excitation at 330 nm makes it a suitable candidate for the building of photoluminescent material.

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Ab Initio Study of Ferroelectric Critical Size of SnTe Low-Dimensional Nanostructures

Nanomaterials ◽

10.3390/nano10040732 ◽

2020 ◽

Vol 10 (4) ◽

pp. 732 ◽

Cited By ~ 1

Author(s):

Takahiro Shimada ◽

Koichiro Minaguro ◽

Tao Xu ◽

Jie Wang ◽

Takayuki Kitamura

Keyword(s):

Density Functional ◽

Critical Size ◽

Density Functional Theory Calculations ◽

Cell Width ◽

Functional Theory ◽

Unit Cells ◽

Principle Density Functional Theory ◽

Low Dimensional ◽

Insight Into ◽

Ferroelectric Perovskite

Beyond a ferroelectric critical thickness of several nanometers existed in conventional ferroelectric perovskite oxides, ferroelectricity in ultimately thin dimensions was recently discovered in SnTe monolayers. This discovery suggests the possibility that SnTe can sustain ferroelectricity during further low-dimensional miniaturization. Here, we investigate a ferroelectric critical size of low-dimensional SnTe nanostructures such as nanoribbons (1D) and nanoflakes (0D) using first-principle density-functional theory calculations. We demonstrate that the smallest (one-unit-cell width) SnTe nanoribbon can sustain ferroelectricity and there is no ferroelectric critical size in the SnTe nanoribbons. On the other hand, the SnTe nanoflakes form a vortex of polarization and lose their toroidal ferroelectricity below the surface area of 4 × 4 unit cells (about 25 Å on one side). We also reveal the atomic and electronic mechanism of the absence or presence of critical size in SnTe low-dimensional nanostructures. Our result provides an insight into intrinsic ferroelectric critical size for low-dimensional chalcogenide layered materials.

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In silico study of binding affinity of nitrogenous bicyclic heterocycles: fragment-to-fragment approach

Ukr. Bioorg. Acta 2021, Vol. 16, N1 - Ukrainica Bioorganica Acta ◽

10.15407/bioorganica2020.02.049 ◽

2020 ◽

Vol 15 (2) ◽

pp. 49-59

Author(s):

Yevheniia Velihina ◽

Nataliya Obernikhina ◽

Stepan Pilyo ◽

Maryna Kachaeva ◽

Oleksiy Kachkovsky ◽

...

Keyword(s):

Amino Acids ◽

Binding Affinity ◽

In Silico ◽

Density Functional ◽

Energy Levels ◽

Aromatic Amino Acids ◽

Electron System ◽

High Energy ◽

Proton Donor ◽

Stabilization Energy

The binding affinity of model aromatic amino acids and heterocycles and their derivatives condensed with pyridine were investigated in silico and are presented in the framework of fragment-to-fragment approach. The presented model describes interaction between pharmacophores and biomolecules. Scrupulous data analysis shows that expansion of the π-electron system by heterocycles annelation causes the shifting up of high energy levels, while the appearance of new the dicoordinated nitrogen atom is accompanied by decreasing of the donor-acceptor properties. Density Functional Theory (DFT) wB97XD/6-31(d,p)/calculations of π-complexes of the heterocycles 1-3 with model fragments of aromatic amino acids, which were formed by π-stack interaction, show an increase in the stabilization energy of π-complexes during the moving from phenylalanine to tryptophan. DFT calculation of pharmacophore complexes with model proton-donor amino acid by the hydrogen bonding mechanism (H-B complex) shows that stabilization energy (DE) increases from monoheterocycles to their condensed derivatives. The expansion of the π-electron system by introducing phenyl radicals to the oxazole cycle as reported earlier [18] leads to a decrease in the stabilization energy of the [Pharm-BioM] complexes in comparison with the annelated oxazole by the pyridine cycle.

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First-Principles Calculation of Conductivity of Ce-C Codoped SnO2 Contacts

Advances in Condensed Matter Physics ◽

10.1155/2021/4346979 ◽

2021 ◽

Vol 2021 ◽

pp. 1-9

Author(s):

Can Ding ◽

Zhenjiang Gao ◽

Xing Hu ◽

Zhao Yuan

Keyword(s):

Charge Density ◽

Lattice Constant ◽

First Principles ◽

Density Functional ◽

Energy Levels ◽

Circuit Breaker ◽

Enthalpy Change ◽

First Principles Calculation ◽

Contact Material ◽

Electronic Density

The contact is the core element of the vacuum interrupter of the mechanical DC circuit breaker. The electrical conductivity and welding resistance of the material directly affect its stability and reliability. AgSnO2 contact material has low resistivity, welding resistance, and so on. This material occupies an important position of the circuit breaker contact material. This research is based on the first-principles analysis method of density functional theory. The article calculated the lattice constant, enthalpy change, energy band, electronic density of state, charge density distribution, population, and conductivity of Ce, C single-doped, and Ce-C codoped SnO2 systems. The results show that Ce, C single doping, and Ce-C codoping all increase the cell volume and lattice constant. When the elements are codoped, the enthalpy change is the largest, and the thermal stability is the best. It has the smallest bandgap, the most impurity energy levels, and the least energy required for electronic transitions. The 4f orbital electrons of the Ce atom and the 2p orbital electrons of C are the sources of impurity energy near the Fermi level. When the elements are codoped, more impurity energy levels are generated at the bottom of the conduction band and the top of the valence band. Its bandgap is reduced so conductivity is improved. From the charge density and population analysis, the number of free electrons of Ce atoms and C atoms is redistributed after codoping. It forms a Ce-C covalent bond to further increase the degree of commonality of electrons and enhance the metallicity. The conductivity analysis shows that both single-doped and codoped conductivity have been improved. When the elements are codoped, the conductivity is the largest, and the conductivity is the best.

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Taguchi-Assisted Optimization Technique and Density Functional Theory for Green Synthesis of a Novel Cu-MOF Derived From Caffeic Acid and Its Anticancerious Activities

Frontiers in Chemistry ◽

10.3389/fchem.2021.722990 ◽

2021 ◽

Vol 9 ◽

Author(s):

Malihe Zeraati ◽

Ali Mohammadi ◽

Somayeh Vafaei ◽

Narendra Pal Singh Chauhan ◽

Ghasem Sargazi

Keyword(s):

Density Functional Theory ◽

Caffeic Acid ◽

Density Functional ◽

Energy Levels ◽

Optimization Technique ◽

Nitrogen Adsorption ◽

High Porosity ◽

Anticancer Activities ◽

Functional Theory ◽

Sem Analyses

In this paper, we have reported an innovative greener method for developing copper-metal organic frameworks (Cu-MOFs) using caffeic acid (CA) as a linker extracted from Satureja hortensis using ultrasonic bath. The density functional theory is used to discuss the Cu-MOF-binding reaction mechanism. In order to achieve a discrepancy between the energy levels of the interactive precursor orbitals, the molecules have been optimized using the B3LYP/6–31G method. The Taguchi method was used to optimize the key parameters for the synthesis of Cu-MOF. FT-IR, XRD, nitrogen adsorption, and SEM analyses are used to characterize it. The adsorption/desorption and SEM analyses suggested that Cu-MOF has a larger surface area of 284.94 m2/g with high porosity. Cu-MOF has shown anticancer activities against the human breast cancer (MDA-MB-468) cell lines, and it could be a potent candidate for clinical applications.

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Stability and magnetic properties of isomorphous substituted Si7-xMnx+

Vietnam Journal of Science and Technology ◽

10.15625/2525-2518/56/1/10506 ◽

2018 ◽

Vol 56 (1) ◽

pp. 64

Author(s):

Nguyen Thanh Tung ◽

Nguyen Thi Mai ◽

Ngo Tuan Cuong

Keyword(s):

Density Functional Theory ◽

Magnetic Properties ◽

Magnetic Moment ◽

Density Functional ◽

Basis Set ◽

Pentagonal Bipyramid ◽

Functional Theory ◽

Electronic Configurations ◽

Method Of Density Functional ◽

Optimized Geometries

The optimized geometries, stability, and magnetic properties of cationic clusters Si7+, Si6Mn+, and Si5Mn2+ have been determined by the method of density functional theory using the B3P86/6-311+G(d) functional/basis set. Their electronic configurations have been analyzed to understand the influence of substituting Si atoms by Mn atoms on the structural and magnetic aspects of Si7+. It is shown that the manganese dopant does not alter the structure of the silicon host but significantly changes its stability and magnetism. In particular, while the magnetic moment of Si7+ is 1 mB, Si5Mn2+ exhibits a strong magnetic moment of 9 mB and that of Si6Mn+ takes a relatively high value of 4 mB. Among studied clusters, the pentagonal bipyramid Si5Mn2+ is assigned as the most stable one.

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Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.13.87 ◽

2017 ◽

Vol 13 ◽

pp. 863-873 ◽

Cited By ~ 8

Author(s):

Vinila N Viswanathan ◽

Arun D Rao ◽

Upendra K Pandey ◽

Arul Varman Kesavan ◽

Praveen C Ramamurthy

Keyword(s):

Molecular Orbital ◽

Architectural Design ◽

Density Functional ◽

Short Circuit ◽

Energy Levels ◽

Photovoltaic Performance ◽

Hole Mobility ◽

Short Circuit Current ◽

Open Circuit ◽

Lowest Unoccupied Molecular Orbital

A series of low band gap, planar conjugated polymers, P1 (PFDTBT), P2 (PFDTDFBT) and P3 (PFDTTBT), based on fluorene and benzothiadiazole, was synthesized. The effect of fluorine substitution and fused aromatic spacers on the optoelectronic and photovoltaic performance was studied. The polymer, derived from dithienylated benzothiodiazole and fluorene, P1, exhibited a highest occupied molecular orbital (HOMO) energy level at −5.48 eV. Density functional theory (DFT) studies as well as experimental measurements suggested that upon substitution of the acceptor with fluorine, both the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels of the resulting polymer, P2, were lowered, leading to a higher open circuit voltage and short circuit current with an overall improvement of more than 110% for the photovoltaic devices. Moreover, a decrease in the torsion angle between the units was also observed for the fluorinated polymer P2 due to the enhanced electrostatic interaction between the fluorine substituents and sulfur atoms, leading to a high hole mobility. The use of a fused π-bridge in polymer P3 for the enhancement of the planarity as compared to the P1 backbone was also studied. This enhanced planarity led to the highest observed mobility among the reported three polymers as well as to an improvement in the device efficiency by more than 40% for P3.

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Electronic and structural features of uranium-doped graphene: DFT study

Main Group Chemistry ◽

10.3233/mgc-210143 ◽

2021 ◽

pp. 1-7

Author(s):

Lina Majeed Haider Al-Haideri ◽

Necla Cakmak

Keyword(s):

Density Functional ◽

Energy Levels ◽

Electronic Conductivity ◽

Structural Features ◽

Level Energy ◽

Size Dependent ◽

The Density Functional Theory ◽

Doped Graphene ◽

Homo And Lumo ◽

Model Size

Electronic and structural features of uranium-doped models of graphene (UG) were investigated in this work by employing the density functional theory (DFT) approach. Three sizes of models were investigated based on the numbers of surrounding layers around the central U-doped region including UG1, UG2, and UG3. In this regard, stabilized structures were obtained and their electronic molecular orbital features were evaluated, accordingly. The results indicated that the stabilized structures could be obtained, in which their electronic features are indeed size-dependent. The conductivity feature was expected at a higher level for the UG3 model whereas that of the UG1 model was at a lower level. Energy levels of the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) were indeed the evidence of such achievement for electronic conductivity features. As a consequence, the model size of UG could determine its electronic feature providing it for specified applications.

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