Li adsorption on a Fullerene–Single wall carbon nanotube hybrid system: Density functional theory approach

In this study, we investigate Li adsorption mechanisms on the C₆₀-SWCNT hybrid system using density functional theory. It is found that the Li adsorption energy of the C₆₀-SWCNT hybrid system is increased in comparison to that of the pure SWCNT. The Li adsorption energy ranges from −1.917 eV to −2.642 eV for the single-Li adsorbed system and from −2.351 eV to −2.636 eV for the double-Li adsorbed system. It is also found that the adsorption energy becomes similar at most positions throughout the structure. In addition, the Li adsorption energy of 31-Li system is calculated to be −1.863 eV, which is significantly lower than the Li–Li binding energy (−1.030 eV). These results infer that Li atoms will be adsorbed on the space 1) between C₆₀ and C₆₀; 2) between SWCNT and C₆₀; 3) the rest of the space (e.g. between SWCNTs), rather than form Li clusters. As more Li atoms are adsorbed onto the C₆₀-SWCNT hybrid system due to such improved Li adsorption capability, the metallic character of the system is enhanced, which is confirmed via the band structure and electronic density of states.     

Density functional theory study on the structure and properties of Si3N4 clusters

The hybrid density functional theory B3LYP with basis sets 6-31G＊ has been used to study on the equilibrium geometries and electronic structures of possible isomers of Si3N4 clusters. 24 possible isomers are obtained. The most stable isomer of Si3N4 is a 3D structure with 7 Si-N bonds and 2 N-N bonds that could beformed by 3 quadrangles. The bond properties of the most stable isomer was analyzed by using natural bond orbital method （NBO）, the results suggest that the charges on Si and N atoms in Si-N bonds are quite large, so theinteraction of N-Si atoms in Si3N4 cluster is of strongly electric interaction. The primary IR and Raman vibrational frequency located at 1033.40 cm^-1, 473.63 cm^-1 respectively. The polarizabilities and hyperpolarizabilities of the most stable isomer are also analyzed.     

Density functional theory study on LaNi4.5Al0.5 hydride phase： electronic properties and sites occupation＊

In this paper the crystal structure, electronic structure and hydrogen site occupation of LaNi4.5Al0.5Hy hydride phase （y = 5.0, 6.0） have been investigated by using full-potential linearized augmented plane wave method. The hydrogen atoms were found to prefer the 6m, 12o and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion, the total density of states at EF increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, H plays a dominant role in the stability of LaNi4.5Al0.5 hydride phase. The smaller the shift of EF towards the higher energy region, the more stable the compounds will be. The obtained results are compared with experimental data and discussed in the light of previous works.     

Density functional theory study on the structure and properties of Si3N4clusters

The hybrid density functional theory B3LYP with basis sets 6-31G· has been used to study on the equilibrium geometries and electronic structures of possible isomers of Si3N4 clusters. 24 possible isomers are obtained. The most stable isomer of Si3N4 is a 3D structure with 7 Si-N bonds and 2 N-N bonds that could be formed by 3 quadrangles. The bond properties of the most stable isomer was analyzed by using natural bond orbital method (NBO), the results suggest that the charges on Si and N atoms in Si-N bonds are quite large, so the interaction of N-Si atoms in Si3N4 cluster is of strongly electric interaction. The primary IR and Raman vibrational frequency located at 1033.40 cm-1, 473.63 cm-1 respectively. The polarizabilities and hyperpolarizabilities of the most stable isomer are also analyzed.     

A density functional theory study on the adsorption of CO and O2 on Cu-terminated Cu2O （111） surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.     

Spatial anisotropy: a method to study anisotropic flow in heavy ion collisions

We introduce a method to study anisotropic flow parameter v_n as a collective probe to Quark Gluon Plasma in relativistic heavy ion collisions. The emphasis is put on the use of the Fourier expansion of initial spatial azimuthal distributions of participant nucleons in the overlapped region. The coefficients ε_n of Fourier expansion are called the spatial anisotropy parameter for the n-th harmonic. We propose that collective dynamics can be studied by v_n/ε_n. In this paper, we will discuss in particular the second (n=2) and the fourth (n=4) harmonics.     

Density functional theory study on activity of α-Fe2O3 in chemical-looping combustion system

The dominant growth planes (0 0 0 1) and (1 1 0 2) have been used to investigate the activity of the natural α-Fe₂O₃ in chemical-looping combustion system based on density functional theory (DFT) calculations. In the chemical-looping combustion system, CO is selected as the probe fuel gas to detect the activities of the different surfaces. CO interacts stronger to Fe₂O₃ (1 1 0 2) than Fe₂O₃ (0 0 0 1). CO can be oxidized into CO₂ species directly on Fe₂O₃ (1 1 0 2) rather than Fe₂O₃ (0 0 0 1). The formation of CO₂ accompanying with a transformation from hematite to magnetite acted as the key step for the reduction process of hematite.     

Density functional theory study of NO2-sensing mechanisms of pure and Ti-dopedWO3 （002） surfaces

Density functional theory (DFT) calculations are employed to explore the NO₂-sensing mechanisms of pure and Ti-doped WO₃ (002) surfaces. When Ti is doped into the WO₃ surface, two substitution models are considered: substitution of Ti for W_6c and substitution of Ti for W_5c. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO₂ on pure and Ti-doped WO₃ (002) surfaces are investigated: adsorptions on 5-fold W (Ti), on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO₂ adsorption structures are both N-end oriented to the surface bridge oxygen O_1c site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO₂, which theoretically proves the experimental observation that Ti doping can greatly increase the WO₃ gas sensor sensitivity to NO₂ gas.     

Density functional study on the bimetallic Ti_mZr_n(n+m ≤ 5) clusters and their interactions with H_2

Equilibrium geometries, stabilities, and electronic properties of small Ti_mZr_n(n + m ≤ 5) clusters were investigated using the density functional method. The ground states were determined, and it was found that the larger clusters and those consisting of more Zr atoms are more stable. The electronic properties of the clusters were discussed based on HOMO-LUMO gaps, vertical ionization potentials(VIP), and vertical electron affinities(VEA). Furthermore, we studied the interactions between those clusters and molecular hydrogen, and found that in all the cases dissociative chemisorptions occurred. According to the chemisorption energies, the pure Zr clusters are relatively more active towards H_2 when compared with the others except Ti_3Zr, which shows the highest activity. The magnetic moments of Ti_mZr_n and Ti_mZr_nH_2 were also compared, and the results show that the hydrogenated clusters have the same or decreased total magnetic moments with respect to the bare clusters except for Ti_3Zr_2.     

Atomic charges of Cl− ions confined in a model Escherichia coli ClC−Cl−/H+ ion exchanger: a density functional theory study

We present extensive semi-empirical and pseudo-potential density functional theory calculations dedicated to analyse the stability, charge density distribution and migration behaviour of Cl^? ions confined in model Escherichia coli (ec) ClC?Cl^?/H⁺ ion-exchangers. Following recent high-resolution crystal structure determination in these kinds of systems, we use a finite-cluster model approach and construct various chemically simplified pore structures made of a glutamate residue ?CH₂?CH₂?COO^? (E148) and its closets 15, 19, 23 and 26 amino acids into which the Cl^? ions will be confined. We reveal the sequence of molecular rearrangements induced on the E148 chain, which blocks the middle of the conduction pathway, leading to the pore opening. The ?CH₂?CH₂?COO^? fragment shows notable variations in its average charge density for small changes in the intra-cellular environment varying from ?0.4e to ?0.3e to ?0.1e in the presence of zero, one and two confined Cl^? ions, respectively, a result that reveals an interesting functionality of the E148 chain during Cl^? conduction. We also obtain complex fluctuations in the ionic charge of the confined Cl^? ions varying from ～?0.7e to ?0.2e, which deviate significantly from the value (?1e) usually used in classical simulations. By attaching a single H species to one of the oxygens of the glutamate group, we obtain that the ?CH₂?CH₂?COOH fragment has now a small effective charge of ～+0.25e. The energy barriers opposing the exit of the Cl^? ions from our considered ion-exchangers vary from 0.65 eV to 4.7 eV, the smallest values being obtained for model structures exhibiting a high degree of flexibility and having protonated E148 fragments. Our results reinforce previous findings and provide additional physical insight, at the atomic level, on the gating process. Finally, we underline the importance of using electronically polarisable force fields to describe the transport of anionic species through this kind of molecular constrictions.     

Hydrazine (N2H4) adsorption on Ni(1 0 0) – Density functional theory investigation

A theoretical study on the structure and adsorption mechanism of hydrazine (N₂H₄) on Ni(1 0 0) are presented. The hydrazine molecule was found to adsorb on the surface through one of its nitrogen atom in its anti-conformation. The charge transfer from hydrazine lone pair orbitals played a key role in the formation of the bonding. The mechanism involved in the bonding was found to reduce the necessity of hyper-conjugation interaction, that reduces the gauche effect found in hydrazine at the gas-phase. Upon adsorption to the surface, the reduced interaction resulted in the promotion of a more favored conformation through its anti-conformation.     

Adsorption of water—methanol mixtures in carbon and aluminosilicate pores: a molecular simulation study

A theoretical study is reported of the adsorption behaviour of water—methanol mixtures in slit carbon and in uncharged alumino-silicate micropores. The adsorption isotherms are obtained for a pore of width of 2 nm and at a temperature of 298 K from grand canonical ensemble Monte Carlo simulations. The results show that the graphite and uncharged silicate surfaces are covered by a dense layer of flatly adsorbed water and methanol molecules having weaker hydrogen bonding. In the interior of the pore, the fluid exhibits bulk-like behaviour with a stronger hydrogen bonded structure. Solvation forces are also calculated as a function of pore size. The positive values found for the solvation force for all pore sizes reflect the hydrophobic interactions of the mixture with the carbon and uncharged alumino-silicate walls.     

Application of the Wiener–Hopf method for describing the propagation of sound in cylindrical and rectangular channels with an impedance jump in the presence of a flow

Exact solutions to problems of the propagation of acoustic modes in lined channels with an impedance jump in the presence of a uniform flow are constructed. Two problems that can be solved by the Wiener- Hopf method—the propagation of acoustic modes in an infinite cylindrical channel with a transverse impedance jump and the propagation of acoustic modes in a rectangular channel with an impedance jump on one of its walls—are considered. On the channel walls, the Ingard–Myers boundary conditions are imposed and, as an additional boundary condition in the vicinity of the junction of the linings, the condition expressing the finiteness of the acoustic energy. Analytical expressions for the amplitudes of the transmitted and reflected fields are obtained.     

Density functional theory study of Ir atom deposited on γ-Al2O3 (001) surface

Iridium adsorption on γ-Al₂O₃ (001) surface has been studied using the ab initio calculation method and the electronic structures of the bare and the Ir adsorbed γ-Al₂O₃ (001) surfaces have been analyzed. By modeling different adsorption sites, one can conclude that the energetically most favorable sites for the Ir are the top sites of the O atoms at the γ-Al₂O₃ (001) surface terminated with octahedral Al. Charge redistribution around the Ir atom adsorbed on the surface improves the activity of the Ir atom as a catalyst.     

Adsorption of chlorine on Ru(0001)—A combined density functional theory and quantitative low energy electron diffraction study

Chlorine adsorption on Ru(0001) surface has been studied by a combined density functional theory (DFT) and quantitative low energy electron diffraction (LEED) approach. The (√3 × √3)R30°-Cl phase with Θ_Cl = 1/3 ML and chlorine sitting in fcc sites has been identified by DFT calculations as the most stable chlorine adsorbate structure on Ru(0001) with an adsorption energy of ? 220 kJ/mol. The atomic geometry of (√3 × √3)R30°-Cl was determined by quantitative LEED. The achieved agreement between experimental and simulated LEED data is quantified by a Pendry factor of r_P = 0.19 for a fcc adsorption site with a Cl-Ru bond length of 2.52 Å. At chlorine coverages beyond 1/3 ML LEED reveals diffuse diffraction rings, indicating a continuous compression of the hexagonal Cl overlayer with a preferred average Cl–Cl distance of 4.7 Å in the (√3 × √3)R30°-Cl, Θ_Cl = 1/3 ML phase towards 3.9 Å at saturation coverage of 0.48 ML.     

Co-adsorption of O_2 and H_2O on α-uranium(110) surface:A density functional theory study

First-principles calculations based on density functional theory corrected by Hubbard parameter U(DFT+U) are applied to the study on the co-adsorption of O2 and H_2O molecules to α-U(110) surface. The calculation results show that DFT+U method with Ueff= 1.5 e V can yield the experimental results of lattice constant and elastic modulus of α-uranium bulk well. Of all 7 low index surfaces of α-uranium, the(001) surface is the most stable with lowest surface energy while the(110) surface possesses the strongest activity with the highest surface energy. The adsorptions of O_2 and H_2O molecules are investigated separated. The O_2 dissociates spontaneously in all initial configurations. For the adsorption of H_2O molecule,both molecular and dissociative adsorptionsoccur. Through calculations of co-adsorption, it can be confirmed that the inhibition effect of O_2 on the corrosion of uranium by water vapor originates from the preferential adsorption mechanism,while the consumption of H atoms by O atoms exerted little influence on the corrosion of uranium.     

The exterior gravitational field of a charged spinning source in the poincaré gauge theory: A Kerr-newman metric with dynamic torsion

We present a new exact solution of the Poincaré gauge theory, namely a charged Kerr-NUT metric with an effective cosmological constant which is consistently coupled to a dynamic torsion field. The solution is given in terms of an orthonormal basis in Boyer-Lindquist coordinates and depends on the constants m₀ (mass), j₀ (angular momentum), q₀ (electric charge), and n₀ (NUT parameter). Whereas m₀,j₀, and q₀ can be specified arbitrarily, the NUT parameter and the effective cosmological constant are determined by the coupling constants of our model. The torsion of the solution is centered around the coordinate origin and vanishes asymptotically for large radial distance. For n₀=0, we find the exterior gravitational field of a charged spinning source.