Density functional theory study of B- and Si-doped carbons and their adsorption interactions with sulfur compounds

Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Calculation of microscopic nuclear level densities based on covariant density functional theory

In this study,a microscopic method for calculating the nuclear level density(NLD)based on the covariant density functional theory(CDFT)is developed.The particle-hole state density is calculated by a combinatorial method using single-particle level schemes obtained from the CDFT,and the level densities are then obtained by considering collective effects such as vibration and rotation.Our results are compared with those of other NLD models,including phenomenological,microstatisti-cal and nonrelativistic Hartree–Fock–Bogoliubov combinatorial models.This comparison suggests that the general trends among these models are essentially the same,except for some deviations among the different NLD models.In addition,the NLDs obtained using the CDFT combinatorial method with normalization are compared with experimental data,including the observed cumulative number of levels at low excitation energies and the measured NLDs.The CDFT combinatorial method yields results that are in reasonable agreement with the existing experimental data.

Optimized numerical density functional theory calculation of rotationally symmetric jellium model systems

In real space density functional theory calculations,the effective potential depends on the electron density,requiring self-consistent iterations,and numerous integrals at each step,making the process time-consuming.In our research,we propose an optimization method to expedite density functional theory(DFT)calculations for systems with large aspect ratios,such as metallic nanorods,nanowires,or scanning tunneling microscope tips.This method focuses on employing basis set to expand the electron density,Coulomb potential,and exchange-correlation potential.By precomputing integrals and caching redundant results,this expansion streamlines the integration process,significantly accelerating DFT computations.As a case study,we have applied this optimization to metallic nanorod systems of various radii and lengths,obtaining corresponding ground-state electron densities and potentials.

Charge self-consistent dynamical mean field theory calculations incombination with linear combination of numerical atomic orbitalsframework based density functional theory

We present a formalism of charge self-consistent dynamical mean field theory(DMFT)in combination with densityfunctional theory(DFT)within the linear combination of numerical atomic orbitals(LCNAO)framework.We implementedthe charge self-consistent DFT+DMFT formalism by interfacing a full-potential all-electron DFT code with threehybridization expansion-based continuous-time quantum Monte Carlo impurity solvers.The benchmarks on several 3d,4fand 5f strongly correlated electron systems validated our formalism and implementation.Furthermore,within the LCANOframework,our formalism is general and the code architecture is extensible,so it can work as a bridge merging differentLCNAO DFT packages and impurity solvers to do charge self-consistent DFT+DMFT calculations.

Local thermal conductivity of inhomogeneous nano-fluidic films:A density functional theory perspective

Combining the mean field Pozhar-Gubbins(PG)theory and the weighted density approximation,a novel method for local thermal conductivity of inhomogeneous fluids is proposed.The correlation effect that is beyond the mean field treatment is taken into account by the simulation-based empirical correlations.The application of this method to confined argon in slit pore shows that its prediction agrees well with the simulation results,and that it performs better than the original PG theory as well as the local averaged density model(LADM).In its further application to the nano-fluidic films,the influences of fluid parameters and pore parameters on the thermal conductivity are calculated and investigated.It is found that both the local thermal conductivity and the overall thermal conductivity can be significantly modulated by these parameters.Specifically,in the supercritical states,the thermal conductivity of the confined fluid shows positive correlation to the bulk density as well as the temperature.However,when the bulk density is small,the thermal conductivity exhibits a decrease-increase transition as the temperature is increased.This is also the case in which the temperature is low.In fact,the decrease-increase transition in both the small-bulk-density and low-temperature cases arises from the capillary condensation in the pore.Furthermore,smaller pore width and/or stronger adsorption potential can raise the critical temperature for condensation,and then are beneficial to the enhancement of the thermal conductivity.These modulation behaviors of the local thermal conductivity lead immediately to the significant difference of the overall thermal conductivity in different phase regions.

Langmuir-Schaefer Film Investigation and Density Functional Theory Band Gap Calculations of Calix[n]arene-Para-Aminobenzoic Acid for Drug Nanosensor Application

Calix[n]arenes was utilized to detect PABA,the primary sunscreen component.This study investigates the interaction of calix[4]arene(C4),calix[6]arene(C6),and PABA using the Langmuir method and first-principle density functional theory(DFT).Using the Langmuir-Schaefer(LS)technique,an ultrathin film composed of calix[n]arenes and their complexes with PABA was deposited on various substrates.Based on the Langmuir study,the PABA molecule was bonded to the lower rims of both C4 and C6 with the host-guest ratio of 1:1.All of the LS films formed were then characterized by ultravioletvisible spectroscopy(UV-Vis),Fourier-transform infrared spectroscopy(FTIR)and carbon,hydrogen,nitrogen,sulfur elemental analyzer(CHNS).The band gap reduction obtained in the DFT study denotes the charge transfer interaction with promising reactivity between the calix[n]arenes and PABA.The sensing of PABA by C4 and C6 is successful based on the formation of bonding between them due to the hosts’effective trapping capacity.The outcomes of this study could be applied to drug delivery systems for future pharmaceutical and medical applications.

Sensitivity impacts owing to the variations in the type of zero-range pairing forces on the fission properties using the density functional theory

Using the Skyrme density functional theory,potential energy surfaces of^(240)Pu with constraints on the axial quadrupole and octupole deformations(q_(20)and q_(30))were calculated.The volume-like and surface-like pairing forces,as well as a combination of these two forces,were used for the Hartree–Fock–Bogoliubov approximation.Variations in the least-energy fission path,fission barrier,pairing energy,total kinetic energy,scission line,and mass distribution of the fission fragments based on the different forms of the pairing forces were analyzed and discussed.The fission dynamics were studied based on the timedependent generator coordinate method plus the Gaussian overlap approximation.The results demonstrated a sensitivity of the mass and charge distributions of the fission fragments on the form of the pairing force.Based on the investigation of the neutron-induced fission of^(239)Pu,among the volume,mixed,and surface pairing forces,the mixed pairing force presented a good reproduction of the experimental data.

A novel algorithm for evaluating cement azimuthal density based on perturbation theory in horizontal well

Cement density monitoring plays a vital role in evaluating the quality of cementing projects,which is of great significance to the development of oil and gas.However,the presence of inhomogeneous cement distribution and casing eccentricity in horizontal wells often complicates the accurate evaluation of cement azimuthal density.In this regard,this paper proposes an algorithm to calculate the cement azimuthal density in horizontal wells using a multi-detector gamma-ray detection system.The spatial dynamic response functions are simulated to obtain the influence of cement density on gamma-ray counts by the perturbation theory,and the contribution of cement density in six sectors to the gamma-ray recorded by different detectors is obtained by integrating the spatial dynamic response functions.Combined with the relationship between gamma-ray counts and cement density,a multi-parameter calculation equation system is established,and the regularized Newton iteration method is employed to invert casing eccentricity and cement azimuthal density.This approach ensures the stability of the inversion process while simultaneously achieving an accuracy of 0.05 g/cm^(3) for the cement azimuthal density.This accuracy level is ten times higher compared to density accuracy calculated using calibration equations.Overall,this algorithm enhances the accuracy of cement azimuthal density evaluation,provides valuable technical support for the monitoring of cement azimuthal density in the oil and gas industry.

Robustness of the octupole collectivity in 144Ba within the cranking covariant density functional theory in 3D lattice

The octupole deformation and collectivity in octupole double-magic nucleus 144Ba are investigated using the Cranking covariant density functional theory in a three-dimensional lattice space.The reduced B(E3)transition probability is implemented for the first time in semiclassical approximation based on the microscopically calculated electric octupole moments.The available data,including the I-ωrelation and electric transitional probabilities B(E2)and B(E3)are well reproduced.Furthermore,it is shown that the ground state of 144Ba exhibits axial octupole and quadrupole deformations that persist up to high spins(I≈24h).

Study the Structural, Electronic, Optical Properties of CZTS Compound after Doping Ba at Zn Site and Si at Sn Site Using Density Functional Theory (DFT)

The structural, electronic, and optical properties of Cu2Zn1−xBaxSn1−ySiyS4 compounds have been calculated using GGA-PBE function within the framework of Density Functional Theory (DFT). In the present work, lattice parameters remained the same, that is tetragonal crystal structure for 0% and 100% doping concentration. The electronic band gap of Cu2Zn1−xBaxSn1−ySiyS4 compounds has been gradually increased for continuous increment of doping concentration where the highest electronic band gap is 1.117 eV for Cu2BaSiS4 structure. Moreover, the band gap changes from direct to indirect band gap with the increase of doping concentration in the parent compound. The absorption coefficient has been found to be high (> 104 cm−1) in UV-region for all the doping concentration which makes the studied compound as a potential candidate of absorber layer in the UV detector. The theoretical study of the effect of double doping in the CZTS compound is very interesting for improving the quality of it and it would be a reference for the theoretical and experimental researchers.

Density functional theory study of influence of impurity on electronic properties and reactivity of pyrite

The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory（DFT）,and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.

Density functional theory study on natural hydrophobicity of sulfide surfaces

Adsorption of water on sulfide surfaces and natural floatability of sulfide minerals were studied using density functional theory （DFT） method. All computational models were built in a vacuum environment to eliminate the effects of oxygen and other factors. H2O molecule prefers to stay with pyrite and sphalerite surfaces rather than water, whereas for galena, chalcocite, stibnite, and molybdenite, H2O molecule prefers to stay with water rather than the mineral surfaces. On the other hand, pyrite surface favors N2 more than water, while sphalerite surface cannot adsorb N2. These results show that galena, stibnite, chalcocite, and molybdenite are hydrophobic, while sphalerite is hydrophilic. Although pyrite has certain hydrophilicity, it tends to be aerophilic because the reaction of pyrite with H2O is weaker than pyrite with N2. Thus, pyrite, galena, chalcocite, stibnite and molybdenite all have natural floatability.

Density Function Theory Study on Effects of Different Energetic Substituent Groups and Bridge Groups on Performance of Carbon-Linked Ditetrazole 2N-Oxides

Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.

Modeling Photovoltaic Performances of BTBPD-PC61BM System via Density Functional Theory Calculations

Designing and fabricating high-performance photovoltaic devices have remained a major challenge in organic solar cell technologies. In this work, the photovoltaic performances of BTBPD-PC61BM system were theoretically investigated by means of density functional theory calculations coupled with the Marcus charge transfer model in order to seek novel photovoltaic systems. Moreover, the hole-transfer properties of BTBPD thin-film were also studied by an amorphous cell with 100 BTBPD molecules. Results revealed that the BTBPD- PC61BM system possessed a middle-sized open-circuit voltage of 0.70 V, large short-circuit current density of 16.874 mA/cm2, large fill factor of 0.846, and high power conversion effi- ciency of 10%. With the Marcus model, the charge-dissociation rate constant was predicted to be as fast as 3.079×10^13 s^-1 in the BTBPD-PC61BM interface, which was as 3-5 orders of magnitude large as the decay （radiative and non-radiative） rate constant （108-10^10 s^-1）, indicating very high charge-dissociation efficiency （-100%） in the BTBPD-PC61BM system. Furthermore, by the molecular dynamics simulation, the hole mobility for BTBPD thin-film was predicted to be as high as 3.970× 10^-3 cm^2V^-1s^-1, which can be attributed to its tight packing in solid state.

Density Functional Theory Study on Electronic and Magnetic Properties of Mn-doped （MgO）n （n=2-10） Clusters

We study the geometries, stabilities, electronic and magnetic properties of （MgO）n （n=2-10） clusters doped with a single Mn atom using the density functional theory with the gener- alized gradient approximation. The optimized geometries show that the impurity Mn atom prefers to replace the Mg atom which has low coordination number in all the lowest-energy MnMgn-1On （n=2-10） structures. The stability analysis clearly represents that the average binding energies of the doped clusters are larger than those of the corresponding pure （MgO）n clusters. Maximum peaks of the second order energy differences are observed for MnMg~_1On clusters at n=6, 9, implying that these clusters exhibit higher stability than their neighboring clusters. In addition, all the Mn-doped Mg clusters exhibit high total magnetic moments with the exception of MnMgO2 which has 3.00μB. Their magnetic behavior is attributed to the impurity Mn atom, the charge transfer modes, and the size of MnMgn- 1On clusters.

Density Functional Theory Calculations of Charge-Induced Spin Polarization in Pentacene

Based on density functional theory （DFT） calculations, we investigate the spin-related properties of spinless-hole injected organic molecule pentacene （Pc）. DFT calculations reveal that there is spontaneous spin polarization in Pc when spinless-hole is injected. The chargeinduced magnetic moment of Pc increases linearly with the increasing of the extra hole charge amount and its maximum can be up to 1 μB per injected spinless-hole per Pc molecule. The magnetic moment is expected due to the injected unpaired charge. The injected hole will preferably ll the spin-splitted carbon pz orbitals, which makes the Pc molecule spin polarize.

Electronic Structure Research on Lattice Stability of V, Nb, and Ta by Density Functional Theory

The difference of energy and electronic structure of V, Nb, and Ta in different crystalline structures were investigated by different methods in density functional theory （DFT）. Lattice constants, total energies, and densities of states of these metals were calculated using the plane-wave pseudopotential method in DFT. Results were compared with those of projector augmented wave method, CALPHAD method, and experiments. Total energy and electronic structure analyses showed that valence electrons mostly transferred from s to p or d state, changing obviously with both the crystal structure and the elemental period number from V to Ta and leading to stronger cohesion, higher cohesive energy and more stable lattice of heavier metals.

Insights into SO_2 and H_2O co-adsorption on Cu(100) surface with calculations of density functional theory

The co-adsorption behaviors of SO2 and H2 O on face-centered cubic Cu（100） ideal surface were studied using the GGA-r PBE method of density functional theory（DFT） with slab models. The optimized structures of single H2 O and SO2 on Cu（100） surface were calculated at the coverage of 0.25 ML（molecular layer） and 0.5 ML. The results show that there was no obvious chemical adsorption of them on Cu（100） surface. The adsorbed structures, adsorption energy and electronic properties including difference charge density, valence charge density, Bader charge analysis and partial density of states（PDOS） of co-adsorbed structures of H2 O and SO2 were investigated to illustrate the interaction between adsorbates and surface. H2 O and SO2 can adsorb on surface of Cu atoms chemically via molecule form at the coverage of 0.25 ML, while H2 O dissociated into OH adsorbed on surface and H bonded with SO2 which keeps away from surface at the coverage of 0.5 ML.

Methylation of toluene with methanol over HZSM-5:A periodic density functional theory investigation

Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ortho and geminal positions via a concerted or stepwise pathway.For the concerted pathway,the calculated free energy barriers for the para,meta,ortho and geminal methylation reactions were 167,138,139 and 183 kJ/mol,respectively.For the stepwise pathway,the dehydration of methanol was found to be the rate-determining step with a free energy barrier of145 kj/mol,whereas the free energy barriers for the methylation of toluene at its para,meta,ortho and geminal positions were 127,105,106 and 114 kj/mol,respectively.Both pathways led to the formation of C8H11^＋ species as important intermediates,which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation.Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C8H11^＋ species to the carbon of the methyl group,with calculated energy barriers of 136,132 and134 kj/mol for the para,meta and ortho C8H11^＋ species,respectively.The calculated free energy barriers for the formation of para-,meta- and ortho-xylene indicated that the formation of the para-xylene had the highest energy barrier for both pathways.

Interactions of Anionic and Neutral Serine with Pure and Metal-doped Graphene Studied by Density Functional Theory

We present a theoretical study of interactions of anionic and neutral serine （Ser） on pure or metal-doped graphene surfaces using density functional theory calculations. Interactions of both types of Ser with the pure graphene surface show weak non-covalent interactions due to the formation of-COOH…π, -COO^-…π, and -OH…π interactions. On metal- doped graphene, covalent interactions to the surface dominate, due to the formation of strong metal-O and O-metal-O interactions. Furthermore, the doped Fe, Cr, Mn, A1, or Ti enhances the ability of graphene to attract both types of Ser by a combination of the adsorption energy, the density of states, the Mulliken atomic charges, and differences of electron density. At the same time, the interaction strengths of anionic Ser on various graphene surfaces are stronger than those of neutral Ser. These results provide useful insights for the rational design and development of graphene-based sensors for the two forms of Ser by introducing appropriate doped atoms. Ti and Fe are suggested to be the best choices among all doped atoms for the anionic Ser and neutral Ser, respectively.