The structure and energetics of carbon-nitrogen clusters

The structures and energies of clusters of carbon and nitrogen with up to 12 atoms have been investigated by density functional theory using the hybrid B3LYP functional and the cc-pVTZ basis set. This is the first systematic study of these clusters. Geometries are reported for the lowest energy states at this level of theory. Linear structures tend to be the global minima for clusters containing one or two nitrogen atoms, and patterns in the electronic structure of these clusters are reported. More complex branched structures lie close in energy to the linear conformations and, for clusters greater than six atoms and containing three or more nitrogen atoms, these branched structures are the minimum energy conformers. Comparisons are made with pure carbon and silicon-carbon clusters.     

Shellwise Mackay transformation in iron nanoclusters

Structure and magnetism of iron clusters with up to 641 atoms have been investigated by means of density functional theory calculations including full geometric optimizations. Body-centered cubic (bcc) isomers are found to be lowest in energy when the clusters contain more than about 100 atoms. In addition, another stable conformation has been identified for magic-number clusters, which lies well within the range of thermal energies as compared to the bcc isomers. Its structure is characterized by a close-packed particle core and an icosahedral surface, while intermediate shells are partially transformed along the Mackay path between icosahedral and cuboctahedral geometry. The gradual transformation results in a favorable bcc environment for the subsurface atoms. For Fe55, the shellwise Mackay-transformed morphology is a promising candidate for the ground state.     

Ab initio thermodynamic characteristics of the formation of oxygen vacancies,and boron,carbon, and nitrogen impurity centers in anatase

Using the ab initio projector augmented wave (PAW) method, calculations are performed for the electronic energy-band structure of titanium dioxide having the structure of anatase doped with boron, nitrogen, and carbon. Thermodynamic characteristics are determined for the formation of impurity centers, such as the preference energy for the interstitial position, the energy of impurity oxidation, and the energy of oxygen vacancy formation. It is shown that under the conditions of thermodynamic equilibrium the interstitial position of boron atoms is stable, whereas carbon atoms, depending on the oxygen pressure, can occupy both interstitial positions and substitutional positions of oxygen atoms, and nitrogen atoms replace oxygen atoms. It is shown that the presence of oxygen vacancies promotes the thermodynamic stability of carbon and nitrogen atoms. The obtained densities of electronic states correspond to ESR spectroscopy data, which indicates the presence of spin-polarized electrons in the states of the oxygen vacancy.     

Computation of vector coupling coefficients for atoms with one and two open shells in the Hartree–Fock approximation

A new way to introduce and calculate vector coupling coefficients (VCCs) is proposed for computations in a Hartree–Fock approximation of atoms with one and two open shells. In the case of atoms with one open shell (Roothaan method), the obtained formulas for VCCs are applicable to the calculation of all terms of such atoms without exception. The VCCs are also calculated for a number of configurations of atoms with two open shells (Huzinaga method). The correctness of the obtained VCCs is confirmed by numerous calculations of energies and dipole polarizabilities for atoms with one and two open shells.     

5d过渡金属原子掺杂氮化硼纳米管的第一性原理计算

采用基于密度泛函理论的第一性原理计算方法,研究了当氮化硼纳米管（BNNT）中的B原子和N原子被5d过渡金属原子（Lu,Hf,Ta,W,Re,Os,Ir,Pt,Au,Hg）取代时BNNT的几何结构、电子结构和磁性性质. 作为对比,给出了理想BNNT,B缺陷体系（V_B）和N缺陷体系（V_N）的相应结果. 研究发现：5d原子取代B（B_5d）时体系的局域对称性接近于C_3v,但是取代N（N_5d）时体系的局域对称性偏离C_3v对称性较大;利用相同的5d原子进行掺杂时,B_5d的成键能比N_5d的成键能大;对于B_5d或者N_5d,其成键能基本上随着5d原子的原子序数的增大而降低;掺杂体系中出现了明显的杂质能级,给出了态密度等结果;不同掺杂情况的磁矩不同,取代B 时体系的总磁矩呈现出较强的规律性. 利用对称性和分子轨道理论解释了5d原子取代B时杂质能级的产生和磁性的变化规律. 关键词： 第一性原理计算 5d过渡金属原子 氮化硼纳米管 密度泛函理论     

Electron energy loss spectra near structural defects in TiN and TiC

In this study, we use first principles multiple scattering calculations on atomic clusters to show how the carbon and nitrogen K-edge fine structures are modified in the vicinity of structural defects in TiN and TiC. Changes in the electron energy loss spectra are due to changes in the atomic structure of the first atomic shells around the absorbing atom. Two different kinds of defects, which both modify the structure of these atomic shells, are investigated here. In a first part, we describe a method which correctly takes into account the statistical spatial distribution of nitrogen vacancies in a TiN cluster. We study the influence of vacancy concentration on the shape of the nitrogen K-edge spectra and we find that vacancies mainly affect the height of the second peak of the spectra. This peak decreases when the number of vacancies in the second nitrogen shell increases. In a second part, we study the carbon K-edge spectrum modification near stacking faults in TiC. Two different stacking faults are studied. These two-dimensional defects are responsible for changes in the position of the carbon as well as titanium atoms of the atomic shells centered on the absorbing carbon atom. The shape of the spectra is strongly modified near the stacking faults and several peaks are affected by these modifications. We show that these fine structure modifications only concern the very first carbon atomic layers near the two-dimensional defects.     

Single photon decay of double hole states in atoms

The probability of single-photon decay of highly excited double hole state of atoms is considered. The concrete calculations are performed in the lowest order of perturbation theory in interelectron interaction for states (2s)^-2 in Ne, (2s)^-2 and (2p)^-2 in double ionized Ar?Ar⁺⁺ and (4d)^-2 in Xe.     

Simple method for obtaining electron scattering phase shifts from energies of an atom in a cavity

We present a simple method for obtaining elastic scattering phase shifts and cross sections from precise ab initio many-body perturbation theory energies of atoms in variable cavities. This method does not require calculations of wave functions of continuum states, can be generalized to many atoms and ions, and is extremely convenient because existing codes developed for energy calculations can be used without modification. The high precision of the method and close agreement with experiment are illustrated on examples of e-Ar and e-Kr scattering. Correlations as well as relativistic corrections are systematically considered.     

Si(111)面上氮原子薄膜的电子态密度第一性原理计算及分析

由于氮原子在Si(1 1 1)表面成键的失配度最小,因此考虑Si(1 1 1)取向上用不同百分比的氮原子钝化硅表面悬挂键.由第一性原理计算结果显示,当Si(1 1 1)表面层中的氮原子含量为75%—100%时,带隙展宽并且有局域陷阱态产生. 我们提出相应的局域电子态模型,从而解释了Si基氮膜光致荧光(PL)发光增强实验的物理机理. 关键词： 第一性原理计算 氮化Si薄膜 PL发光增强 局域陷阱态     

Theoretical study of the migration of the hydrogen atom adsorbed on aluminum nanowire

We study the behavior of a hydrogen atom adsorbed on aluminum nanowire based on density functional theory. In this study, we focus on the electronic structure, potential energy surface (PES), and quantum mechanical effects on hydrogen and deuterium atoms. The activation energy of the diffusion of a hydrogen atom to the axis direction is derived as 0.19 eV from PES calculations. The probability density, which is calculated by including quantum effects, is localized on an aluminum top site in both cases of hydrogen and deuterium atoms of the ground state. In addition, some excited states are distributed between aluminum atoms on the surface of the nanowire. The energy difference between the ground state and these excited states are below 0.1 eV, which is much smaller than the activation energy of PES calculations. Thus using these excited states, hydrogen and deuterium atoms may move to the axial direction easily. We also discuss the electronic structure of the nanowire surface using quantum energy density defined by one of the authors.     

Mössbauer analysis of Fe−N austenites

Analysis of transmission Mössbauer spectra for high nitrogen Fe?N austenites is done in terms of five iron environments dealing with first and second nearest neighbour shells. The similar analysis for Fe?C austenites which displays only three iron environments led to the conclusion that carbon atoms are ordered whereas nitrogen atoms are more randomly distributed.     

Core-level spectroscopy of point defects in single layer h-BN

Electron energy-loss spectroscopy (EELS) is used to analyze single-layered hexagonal boron-nitride with or without point defects. EELS profiles using a 0.1 nm probe clearly discriminate the chemical species of single atoms but show different delocalization of the boron and nitrogen K edges. A monovacancy at the boron site is unambiguously identified and the electronic state of its nearest neighboring nitrogen atoms is examined by energy-loss near edge fine structure analysis, which demonstrates a prominent defect state. Theoretical calculations suggest that the observed prepeak originates from the 1s to lowest unoccupied molecular orbital excitation of dangling nitrogen bonds, which is substantially lowered in energy with respect to the three coordinated nitrogen atoms.     

Silicon carbide nanocones: Computational analysis of chemical shieldings for pristine and boron/nitrogen decorated models

Density functional theory (DFT) calculations were performed to investigate the electronic and structural properties of pristine and boron/nitrogen (B/N) decorated models of a representative silicon carbide nanocone (SiCNC). The atoms of apexes and tips were differently decorated by B/N atoms to make all possible decorations of the investigated SiCNC. The evaluated parameters by the optimization processes and nuclear magnetic resonance (NMR) calculations indicated that the overall and atomic scale properties of the investigated SiCNCs are significantly dependent on the ways of decorations of Si/C atoms by B/N atoms. The Si/C atoms close to the decorated regions also exhibited notable changes in comparison to the pristine model.     

First-Principles Studies on Properties of Boron-Related Impurities in c-BN

We investigate, by first-principles calculations, the pressure dependence of formation enthalpies and defective geometry and bulk modulus of boron-related impurities （VB, Cs, NB, and OB） with different charged states in cubic boron nitride （c-BN） using a supercell approach. It is found that the nitrogen atoms surrounding the defect relax inward in the case of CB, while the nitrogen atoms relax outward in the other cases. These boron-related impurities become much more stable and have larger concentration with increasing pressure. The impurity CB^＋1 is found to have the lowest formation enthalpy, make the material exhibit semiconductor characters and have the bulk modulus higher than ideal c-BN and than those in the cases of other impurities. Our results suggest that the hardness of c-BN may be strengthened when a carbon atom substitutes at a B site.     

Tuning the electronic and magnetic properties of boron nitride nanotubes

Density Functional Theory is used to investigate the effect of altering the B/N ratio and carbon doping on the electronic and magnetic structure of zigzag, (7, 0) and armchair (5, 5) boron nitride nanotubes. The calculations indicate that increasing the boron content relative to the nitrogen content significantly reduces the band gap to a value typical of a semiconductor. Calculations of carbon doped semiconducting BN tubes, which have more boron atoms than nitrogen atoms have a net spin and a difference in the density of states at the valence band between the spin up and spin down state.     

Theorie der spontanen Magnetisierung kleiner ferromagnetischer Teilchen

With a modified conception of the Néel sublattices a molecular field theory is developed for small ferromagnetic particles. They are treated as a system of neighboring shells. These are supposed to consist each of atoms with equal average properties and are coupled to the next neighbors by an (exchange-) interaction. To simplify the numerical calculations the model was further modified by taking together all shells of the interior to form a core. Calculations of the temperature dependence of the spontaneous magnetization and of Curie-temperatures have been done for some particle forms and sizes of the f.c.c., b.c.c. and hexagonal lattices. The results are discussed and compared to experimental data of other authors from small particles of nickel, iron and cobalt.     

Structure of endohedral complexes of carbon nanotubes encapsulated with lithium and sodium

The article provides the results of ab initio calculations employing density functional theory of carbon nanotubes that contain clusters of lithium and sodium atoms. Stable positions of interstitial atoms, the electron density distribution in the system and the density of electronic states are determined. It is shown that the amount of charge transferred from the interstitial atoms in a cluster significantly differs from the corresponding value for a single atom. It is established that the density of electronic states of the system at low concentrations of atoms of the introduced element is determined by the electronic structure of a hollow nanotube, and as the concentration of interstitial atoms increases, this quantity becomes virtually independent on the type of alkali metal (lithium or sodium) and the initial type of the nanotube conductivity.     

Collisions of electrons with molecules in excited vibrational-rotational states

Results are presented of calculations of cross sections for scattering of electrons by diatomic molecules in specific excited vibrational-rotational states. The calculations were made using an approximation based on a quantum theory of scattering in a system of several bodies which can be applied to calculations of direct reactions and reactions involving the formation of an intermediate transition complex. Results of calculations of cross sections for collisions of electrons with hydrogen, nitrogen, lithium, sodium, and hydrogen halide molecules are compared with existing experimental data and the results of calculations made by other authors.     

X-ray photoelectron investigation of charge distribution in copper(II) phthalocyanine complexes

The charged states of atoms in unsubstituted copper(II) phthalocyanine (CuPcH₁₆) and hexade-cafluorinated copper(II) phthalocyanine (CuPcF₁₆) complexes and in thin films of them deposited on silicon substrates by vacuum thermal evaporation are investigated by X-ray photoelectron spectroscopy (XPS). The C(1s), N(1s), Cu(2p) core level energies and the charged states of atoms in the studied complexes are calculated using the DFT method. The performed experimental study and theoretical calculations show that the introduction of electron acceptor substituents into benzene rings mostly affects the atoms of benzene rings and insignificantly affects the charge state of nitrogen atoms in the pyrrole ring.     

A tight-binding study of LUMO states in ellipsoidal silicon nanocrystals

In this paper we report on tight-binding calculations of lowest unoccupied molecular orbitals states for silicon ellipsoidal nanocrystals. The electronic structure has been calculated for different nanocrystal shapes either keeping constant or varying the number of silicon atoms. We have found that changing the ellipsoid aspect ratio a non-obvious energy level structure is obtained. The implications for the infrared optical transitions and their relationship with the polarization of the radiation involved are discussed.