Random-phase approximation correlation methods for molecules and solids

Random-phase approximation (RPA) correlation methods based on Kohn–Sham density-functional theory and Hartree–Fock are derived using the adiabatic-connection fluctuation dissipation theorem. It is shown that the correlation energy within the adiabatic-connection fluctuation-dissipation theorem is exact in a Kohn–Sham framework while for Hartree–Fock reference states this is not the case. This shows that Kohn–Sham reference states are probably better suited to describe electron correlation for use in RPA methods than Hartree–Fock reference states. Both, Kohn–Sham and Hartree–Fock RPA methods are related to each other both by comparing the underlying correlation functionals and numerically through the comparison of total energies and reaction energies for a set of small organic molecules.     

Encapsulation of small fullerenes into nitrogenated holey nanotubes: a density functional theory study

Encapsulation of fullerene into nanotubes based on a C₂N sheet, known as nitrogenated holey graphene, was investigated using density functional theory. The structural and electronic properties of these carbon hybrid materials, consisting of nitrogenated holey nanotubes and a small C₂₀ fullerene, were studied. The formation energies showed that encapsulation of the fullerene into the nitrogenated holey nanotube is an exothermic process. To characterise the electronic properties, the electronic band structure and density of states of armchair and zigzag nitrogenated holey nanotubes were calculated. Filling these nanotubes with the C₂₀ fullerene resulted in a p-type semiconducting character. The energy band gap of the nitrogenated holey nanotubes decreased with fullerene encapsulation. The results are indicative of the possibility of band gap engineering by encapsulation of small fullerenes into nitrogenated holey nanotubes.     

The bond force constants and elastic properties of boron nitride nanosheets and nanoribbons using a hierarchical modeling approach

A hierarchical approach bridging the atomistic and nanometric scales is used to compute the elastic properties of boron nitride nanosheets and nanoribbons, examining the effect of sheet size, aspect ratio and anisotropy. The approach consists in obtaining the bond force (force field) constants by dedicated computations based on density functional theory (DFT) and using such constants as input for larger scale structural models solved by finite element analysis (FEA). The bond force constants calculated by DFT are 616.9 N/m for stretching, 6.27×10⁻¹⁹ Nm/rad² for in-plane rotation and 1.32×10⁻¹⁹ Nm/rad² for dihedral rotation. Using these constants, the elastic properties of boron nitride nanosheets and nanoribbons predicted by FEA are almost independent of the sheet size, but strongly dependent on their aspect ratio. The sheet anisotropy increases with increased aspect ratio, with nanoribbons of aspect ratios of 10 exhibiting a ratio of elastic moduli along both in-plane directions of 1.7.     

A periodic DFT study on adsorption of small molecules(CH_4,CO,H_2O,H_2S,NH_3)on the WO_3(001) surface-supported Au

Gas molecules(such as CH4,CO,H2O,H2S,NH_3)adsorption on the pure and Au-doped WO3(001)surface have been studied by Density functional theory calculations with generalized gradient approximation.Based on the the calculation of adsorption energy,we found the most stable adsorption site for gas molecules by comparing the adsorption energies of different gas molecules on the WO3(001)surface.We have also compared the adsorption energy of five different gas molecules on the WO3(001)surface,our calculation results show that when the five kinds of gases are adsorbed on the pure WO3(001)surface,the order of the surface adsorption energy is CO>H2S>CH4>H2O>NH3.And the results show that NH3 is the most easily adsorbed gas among the other four gases adsorbed on the surface of pure WO3(001)surface.We also calculated the five different gases on the Au-doped WO3(001)surface.The order of adsorption energy was found to be different from the previous calculation:CO>CH4>H2S>H2O>NH3.These results provide a new route for the potential applications of Au-doped WO3 in gas molecules adsorption.     

Atomic displacements due to interstitial hydrogen in Cu and Pd

The density functional theory (DFT) is used to study the atomic interactions in transition metal-based interstitial alloys. The strain field is calculated in the discrete lattice model using Kanzaki method. The total energy and hence atomic forces between interstitial hydrogen and transition metal hosts are calculated using DFT. The norm-conserving pseudopotentials for H, Cu and Pd are generated self-consistently. The dynamical matrices are evaluated considering interaction up to first nearest neighbors whereas impurity-induced forces are calculated with M₃₂H shell (where M = Cu and Pd). The atomic displacements produced by interstitial hydrogen at the octahedral site in Cu and Pd show displacements of 7.36% and 4.3% of the first nearest neighbors respectively. Both Cu and Pd lattices show lattice expansion due to the presence of hydrogen and the obtained average lattice expansion ΔV/V = 0.177 for Cu and 0.145 for Pd.      

Adsorption of CO, NH3 and O2 on Fe site of La0.875Sr0.125FeO3 (0 1 0) surface by density function theory calculation

The adsorption of CO, NH₃ and O₂ gas molecules on Fe site of La_0.875Sr_0.125FeO₃ (0 1 0) surface has been investigated based on the density functional theory (DFT) with the spin polarized generalized gradient approximation (GGA). The optimal adsorption orientations as well as the adsorption energies for these molecules adsorption on Fe site of La_0.875Sr_0.125FeO₃ (0 1 0) surface are derived. Results show that adsorption configurations with C-down for CO, N-down for NH₃ are stable. For the O₂ molecule adsorption, the mode with an angle about 120° between the oxygen molecule and La_0.875Sr_0.125FeO₃ (0 1 0) surface is stable.     

AunCu ( n =1-3)二元合金小团簇结构和稳定性的密度泛函研究

采用密度泛函理论(DFT) B3LYP 在SDD基组水平上对AunCu(n =1-3)二元合金小团簇各种可能的构型进行几何优化,预测了各团簇的稳定结构. 并对基态结构进行了研究,计算了平均结合能、最高占据轨道能级和最低空轨道能级以及两者间的能隙.结果表明掺杂Cu原子后使得AunCu(n =1-3)团簇的化学性质更稳定.     

KLL Auger resonant Raman transition in metallic Cu and Ni

High energy resolution KL₂₃L₂₃ Auger spectra of polycrystalline Cu and Ni were measured using photon energies up to about 50 eV above the K-absorption edge and down to 5 eV (Cu KLL) and 4 eV (Ni KLL) below threshold. The spectra show strong satellite structures varying considerably as a function of the photon energy. In the sub-threshold region the linear dispersion of the diagram line energy positions and a distortion of the line shape as a function of photon energy, attributable to the Auger resonant Raman process, is clearly observed, indicating the one-step nature of the Auger emission. These changes in the resonant spectra are interpreted using a simple model based on resonant scattering theory in combination with partial density of states obtained from cluster molecular orbital (DV-Xα) calculations.