Abstract: The electronic structure calculation for the nanoclusters of AsSiTeB/SiAsBTe quaternary semiconductor alloy belonging to the III-V Group elements was performed. Motivation for this research work was to look for accurate electronic and geometric data of small nanoclusters of AsSiTeB/SiAsBTe in the gaseous form. The two clusters, one in the linear form and the other in the bent form, were studied under the framework of Density Functional Theory (DFT) using the B3LYP functional and LANL2DZ basis set with the software packaged Gaussian 16. We have discussed the Optimized Energy, Frontier Orbital Energy Gap in terms of HOMO-LUMO, Dipole Moment, Ionization Potential, Electron Affinity, Binding Energy, Embedding Energy, Density of States (DoS) spectrum for both structures. The important findings of the predicted nanostructures are that these structures have wide band gap energy, where linear structure has band gap energy (Eg) value is 2.375 eV and bent structure (Eg) value is 2.778 eV. Therefore, these structures can be utilized as wide band gap semiconductors. These structures have high electron affinity value of 4.259 eV for the linear structure and electron affinity value of 3.387 eV for the bent structure form. It shows that electron acceptor capability is high for both forms. The widely known application of these compounds is in the light emitting diodes due to their wide band gap nature.
Abstract: This study deals with the structural and electronic properties of ternary PdMnGe Half-Heusler alloy using the full potential linearized augmented plane wave (FP-LAPW) method based on the density functional theory (DFT) as implemented in the WIEN2k package, within the framework of generalized gradient approximation (GGA). Structural parameters, total and partial densities of states were also analyzed. The obtained result shows that the studied material is metallic in GGA treatment. The elastic constants (Cij) show that our compound is ductile, stiff and anisotropic.
Abstract: We study the temperature dependence of the interaction energies (IEs) of X (=Ru, Rh) impurities in Pd, due to the Fermi-Dirac (FD) distribution and the thermal vibration effect by the Debye-Grüneisen model. The n-body (n=2~4) IEs among X impurities in Pd, being used to calculate the internal energies in the free energies of the Pd-rich PdX alloys, are determined uniquely and successively from the lower-order to higher-order, by the full-potential Korringa-Kohn-Rostoker Green’s function method (FPKKR), combined with the generalized gradient approximation in the density functional theory. We found that the temperature dependence of IEs due to the FD distribution, being usually neglected, is very important to reproduce the X-concentration dependence of the observed solvus temperatures of the Pd-rich PdX (X=Ru, Rh) alloys.
Abstract: Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.
Abstract: We present a theoretical investigation on the structural,
electronic properties and vibrational mode of nitrogen impurities
in ZnO. The atomic structures, formation and transition energies
and vibrational modes of (NO3)i interstitial or NO4 substituting
on an oxygen site ZnO were computed using ab initio total energy
methods. Based on Local density functional theory, our calculations
are in agreement with one interpretation of bound-excition
photoluminescence for N-doped ZnO. First-principles calculations
show that (NO3)i defects interstitial or NO4 substituting on an
Oxygen site in ZnO are important suitable impurity for p-type doping
in ZnO. However, many experimental efforts have not resulted in
reproducible p-type material with N2 and N2O doping. by means of
first-principle pseudo-potential calculation we find that the use of NO
or NO2 with O gas might help the experimental research to resolve
the challenge of achieving p-type ZnO.
Abstract: Optical properties of bulk and thin film of 1H-CaAlSi for two directions (1,0,0) and (0,0,1) were studied. The calculations are carried out by Density Functional Theory (DFT) method using full potential. GGA approximation was used to calculate exchange-correlation energy. The calculations are performed by WIEN2k package. The results showed that the absorption edge is shifted backward 0.82eV in the thin film than the bulk for both directions. The static values of the real part of dielectric function for four cases were obtained. The static values of the refractive index for four cases are calculated too. The reflectivity graphs have shown an intensive difference between the reflectivity of the thin film and the bulk in the ultraviolet region.
Abstract: The fundamental issue in understanding the origin and
growth mechanism of nanomaterials, from a fundamental unit is a big
challenging problem to the scientists. Recently, an immense attention
is generated to the researchers for prediction of exceptionally stable
atomic cluster units as the building units for future smart materials.
The present study is a systematic investigation on the stability and
electronic properties of a series of bimetallic (semiconductor-alkaline
earth) clusters, viz., BxMg3 (x=1-5) is performed, in search for
exceptional and/ or unusual stable motifs. A very popular hybrid
exchange-correlation functional, B3LYP along with a higher basis
set, viz., 6-31+G[d,p] is employed for this purpose under the density
functional formalism. The magic stability among the concerned
clusters is explained using the jellium model. It is evident from the
present study that the magic stability of B4Mg3
cluster arises due to
the jellium shell closure.
Abstract: Here, we have shown the reaction of [Cr(ArN(CH2)3NAr)2Cl2] (1) where (Ar = 2,6-Pri
2C6H3) and in presence of NaCp (2) (Cp= C5H5 = cyclopentadien), with a center
coordination η5 interaction between Cp as co-ligand and chromium
metal center, for optimization we used density functional theory
(DFT), under methods, explicitly including electrons correlations, for
the final calculations as MB3LYP (Becke) (Lee–Yang–Parr) level of
theory we used to obtain more exact results. This complex was
calculated as electronic energy for molecular system, because the
calculation accounting all electrons correlations interactions. The
optimised of [Cr(ArN(CH2)3NAr)2(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp = C5H5) was found to be thermally stable. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis
and showed the highest occupied molecular orbital (HOMO) and
lowest occupied molecular orbital LUMO.
Abstract: In this study, nuclear magnetic resonance
spectroscopy and nuclear quadrupole resonance spectroscopy
parameters of 14N (Nitrogen in imidazole ring) in N–H…O hydrogen
bonding for Histidine hydrochloride monohydrate were calculated via
density functional theory. We considered a five-molecule model
system of Histidine hydrochloride monohydrate. Also we examined
the trends of environmental effect on hydrogen bonds as well as
cooperativity. The functional used in this research is M06-2X which
is a good functional and the obtained results has shown good
agreement with experimental data. This functional was applied to
calculate the NMR and NQR parameters. Some correlations among
NBO parameters, NMR and NQR parameters have been studied
which have shown the existence of strong correlations among them.
Furthermore, the geometry optimization has been performed using
M062X/6-31++G(d,p) method. In addition, in order to study
cooperativity and changes in structural parameters, along with
increase in cluster size, natural bond orbitals have been employed.
Abstract: In this paper, we investigated the athermal pressure
behavior of the structural and elastic properties of scheelite BaWO4
phase up to 7 GPa using the ab initio pseudo-potential method. The
calculated lattice parameters pressure relation have been compared
with the experimental values and found to be in good agreement with
these results. Moreover, we present for the first time the investigation
of the elastic properties of this compound using the density functional
perturbation theory (DFPT). It is shown that this phase is
mechanically stable up to 7 GPa after analyzing the calculated elastic
constants. Other relevant quantities such as bulk modulus, pressure
derivative of bulk modulus, shear modulus; Young’s modulus,
Poisson’s ratio, anisotropy factors, Debye temperature and sound
velocity have been calculated. The obtained results, which are
reported for the first time to the best of the author’s knowledge, can
facilitate assessment of possible applications of the title material.
Abstract: We investigated the structure and electronic properties
of the compound Mg1-xBixO with varying concentrations of 0, ¼, ½,
and ¾ x bismuth in the the cesium chloride (CsCl), zinc-blende
(ZnS), nickel arsenide (NiAs) NaCl (rock-salt) and WZ (wurtzite)
phases. We calculated. The calculations were performed using the
first-principles pseudo-potential method within the framework of spin
density functional theory (DFT).
Abstract: The capability of exploiting the electronic charge and
spin properties simultaneously in a single material has made diluted
magnetic semiconductors (DMS) remarkable in the field of
spintronics. We report the designing of DMS based on zinc-blend
ZnO doped with Cr impurity. The full potential linearized augmented
plane wave plus local orbital FP-L(APW+lo) method in density
functional theory (DFT) has been adapted to carry out these
investigations. For treatment of exchange and correlation energy,
generalized gradient approximations have been used. Introducing Cr
atoms in the matrix of ZnO has induced strong magnetic moment
with ferromagnetic ordering at stable ground state. Cr:ZnO was found
to favor the short range magnetic interaction that
reflect tendency of Cr clustering. The electronic structure of ZnO is
strongly influenced in the presence of Cr impurity atoms where
impurity bands appear in the band gap.
Abstract: Using the first-principles full-potential linearized
augmented plane wave plus local orbital (FP-LAPW+lo) method
based on density functional theory (DFT), we have investigated the
electronic structure and magnetism of full Heusler alloys Co2ZrGe
and Co2NbB. These compounds are predicted to be half-metallic
ferromagnets (HMFs) with a total magnetic moment of 2.000 B per
formula unit, well consistent with the Slater-Pauling rule.
Calculations show that both the alloys have an indirect band gaps, in
the minority-spin channel of density of states (DOS), with values of
0.58 eV and 0.47 eV for Co2ZrGe and Co2NbB, respectively.
Analysis of the DOS and magnetic moments indicates that their
magnetism is mainly related to the d-d hybridization between the Co
and Zr (or Nb) atoms. The half-metallicity is found to be relatively
robust against volume changes. In addition, an atom inside molecule
AIM formalism and an electron localization function ELF were also
adopted to study the bonding properties of these compounds, building
a bridge between their electronic and bonding behavior.
As they have a good crystallographic compatibility with the lattice of
semiconductors used industrially and negative calculated cohesive
energies with considerable absolute values these two alloys could be
promising magnetic materials in the spintronic field.
Abstract: Physical properties of uranium dinitride (UN2) were
investigated in detail using first principle calculations based on
density functional theory (DFT). To study the strong correlation
effects due to 5f uranium valence electrons, the on-site coulomb
interaction correction U via the Hubbard-like term (DFT+U) was
employed. The UN2 structural, mechanical and thermodynamic
properties were calculated within DFT and Various U of DFT+U
approach.
The Perdew–Burke–Ernzerhof (PBE.5.2) version of the
generalized gradient approximation (GGA) is used to describe the
exchange-correlation with the projector-augmented wave (PAW)
pseudo potentials.
A comparative study shows that results are improved by using the
Hubbard formalism for a certain U value correction like the structural
parameter. For some physical properties the variation versus
Hubbard-U is strong like Young modulus but for others it is weakly
noticeable such as bulk modulus.
We noticed also that from U=7.5 eV, elastic results don’t agree
with the cubic cell because of the C44 values which turn out to be
negative.
Abstract: In this work, we study the behavior of introducing
atomic size vacancy in a graphene nanoribbon superlattice. Our
investigations are based on the density functional theory (DFT) with
the Local Density Approximation in Atomistix Toolkit (ATK). We
show that, in addition to its shape, the position of vacancy has a
major impact on the electrical properties of a graphene nanoribbon
superlattice. We show that the band gap of an armchair graphene
nanoribbon may be tuned by introducing an appropriate periodic
pattern of vacancies. The band gap changes in a zig-zag manner
similar to the variation of band gap of a graphene nanoribbon by
changing its width.
Abstract: A novel new vanadium (IV) complexes incorporating the chelating diamido cyclopentadienyl {ArN(CH2)3NAr)}2-((ηn-Cp)Cp)} (Ar = 2,6-Pri2C6H3)(Cp = C5H5 and n = 1,2,3,4 and 5) have been studied with calculation of the properties of species involved in various of cyclopentadienyl reaction. These were carried out under investigation of density functional theory (DFT) calculation, and comparing together. Other methods, explicitly including electron correlation, are necessary for more accurate calculations; MB3LYP (Becke) (Lee–Yang–Parr) level of theory often being used to obtain more exact results. These complexes were estimated of electronic energy for molecular system, because it accounts for all electron correlation interactions.
The optimised of [V(ArN(CH2)3NAr)2Cl(η5-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) was found to be thermally more stable than others of vanadium cyclopentadienyl. In the meantime the complex [V(ArN(CH2)3NAr)2Cl(η1-Cp)] (Ar = 2,6-Pri2C6H3 and Cp= C5H5) which is showed a low thermal stability in case of the just one carbon of cyclopentadienyl can be insertion with vanadium metal centre. By using Dewar-Chatt-Duncanson model, as a basis of the molecular orbital (MO) analysis and showed the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital LUMO.
Abstract: Using first-principles methods based on density functional theory and pseudopotentials, we have performed a details study of native defects in ZnO. Native point defects are unlikely to be cause of the unintentional n-type conductivity. Oxygen vacancies,
which considered most often been invoked as shallow donors, have high formation energies in n-type ZnO, in edition are a deep donors. Zinc interstitials are shallow donors, with high formation energies in n-type ZnO, and thus unlikely to be responsible on their own for unintentional n-type conductivity under equilibrium conditions, as well as Zn antisites which have higher formation energies than zinc interstitials. Zinc vacancies are deep acceptors with low formation energies for n-type and in which case they will not play role in p-type coductivity of ZnO. Oxygen interstitials are stable in the form of electrically inactive split interstitials as well as deep acceptors at the octahedral interstitial site under n-type conditions. Our results may provide a guide to experimental studies of point defects in ZnO.
Abstract: Using ab initio theoretical calculations, we present
analysis of fragmentation process. The analysis is performed in two
steps. The first step is calculation of fragmentation energies by ab
initio calculations. The second step is application of the energies to
kinetic description of process. The energies of fragments are
presented in this paper. The kinetics of fragmentation process can be
described by numerical models. The method for kinetic analysis is
described in this paper. The result - composition of fragmentation
products - will be calculated in future. The results from model can be
compared to the concentrations of fragments from mass spectrum.
Abstract: Zirconium diamine and triamine complexes can possess biological activities. These complexes were synthesised via the reaction of equimolar quantities of 1,10-phenanthroline {NC3H3(C6H2)NC3H3} (L1) or 4-4-amino phenazone {ONC6H5(NH)CH(NH2} (L2) or diphenyl carbizon {HNNCO(NH)2(C6H5)} (L3) with a Zirconium Salt {ZrOCl2} in a 1:1 ratio to form complexes [{NC3H3(C6H2)NC3H3}ZrOCl2}] [ZrOCl2L1], [{(O2NC6H4(NH)(NH2)}ZrOCl2] [ZrOCl2L2] and [{HNNCO(NH)2(C6H5)ZrOCl2}] [ZrOCl2L3] respectively. They were characterised using Fourier Transform Infrared (FT-IR) and UV-Visible spectroscopy. Also a variable temperature study of these complexes was completed, using UV-Visible spectroscopy to observe electronic transitions under temperature control. Also a DFT study was done on these complexes via the information from FT-IR and UV-Visible spectroscopy.
These complexes were found to show different inhibition to the growth of bacterial strains of Bacillus spp. & Klebsiella spp. & E. coli & Proteus spp. & Pseudomona spp. at different concentrations (0.001, 0.2 and 1M). For better understanding these complexes were examined by using a Density Functional Theory (DFT) calculation.
Abstract: In this paper, four carbazole-based D-D-π-A organic
dyes code as CCT2A, CCT3A, CCT1PA and CCT2PA were reported.
A series of these organic dyes containing identical donor and
acceptor group but different π-system. The effect of replacing of
thiophene by phenyl thiophene as π-system on the physical
properties has been focused. The structural, energetic properties and
absorption spectra were theoretically investigated by means of
Density Functional Theory (DFT) and Time-Dependent Density
Functional Theory (TD-DFT). The results show that nonplanar
conformation due to steric hindrance in donor part (cabazolecarbazole
unit) of dye molecule can prevent unfavorable dye
aggregation. By means of the TD-DFT method, the absorption
spectra were calculated by B3LYP and BHandHLYP to study the
affect of hybrid functional on the excitation energy (Eg). The results
revealed the increasing of thiophene units not only resulted in
decreasing of Eg, but also found the shifting of absorption spectra to
higher wavelength. TD-DFT/BHandHLYP calculated results are
more strongly agreed with the experimental data than B3LYP
functions. Furthermore, the adsorptions of CCT2A and CCT3A on the
TiO2 anatase (101) surface were carried out by mean of the chemical
periodic calculation. The result exhibit the strong adsorption energy.
The calculated results provide our new organic dyes can be
effectively used as dye for Dye Sensitized Solar Cell (DSC).