Nuclear spin-lattice relaxation of impurities in ferromagnetic iron

Due to the development of Green's function method the calculation of the nuclear spin-lattice relaxation time of impurities in ferromagnets has become feasible in the last years. We present the result of calculations for allsp andd impurities in ferromagnetic iron. The calculations are based on the density functional formalism. They well, reproduce the experimental trend of the relaxation timeT ₁ for bothsp andd impurities. By decomposing the relaxation rate into various contributions, we explain the observed systematic behavior ofT ₁ T in terms of the local electronic structure.     

Covalency in the electronic structure of Fe3O4: An ultraviolet inverse photoemission investigation

The unoccupied electronic structure of an opend-shell transition metal oxide, namely Fe₃O₄, has been addressed by measuring ultraviolet angle-integrated inverse photoemission (IP) spectra acquired in the isochromat mode (hv=10.2-24 eV). Exploitation of photon energy dependence of symmetry-projected IP cross-sections and comparison with the O 1s X-ray absorption spectrum allow us to recognize a strong covalent admixture of Fe [3d; 4 (sp)]-and O (2p)-derived states in this compound.     

X-ray absorption and emission spectroscopic investigation of Mn doped ZnO films

The electronic structure of (Zn,Mn)O films with different Mn concentrations has been investigated by element-selective soft X-ray absorption and emission spectroscopy. The band gap narrowing of (Zn,Mn)O with increase of Mn concentration (<20% Mn) is attributed to the Mn doping and sp-d exchange interactions. According to analysis of the O Kα and resonant Mn L_2,3 X-ray emission spectra, the splitting of Mn 3d subbands is related to Mn-derived states. It indicates that ferromagnetic coupling in (Zn,Mn)O can be taken into account to be carrier-induced. The presence of antiferromagnetism in the heavier Mn-doped films can be explained in terms of the existence of MnO secondary phases.     

Photoemission study of the electronic structure of Mn in Ag

The electronic structure of the (001) surfaces of Ag and two Ag–Mn alloys (5 and 10 at.% Mn) was studied using angle-resolved photoelectron spectroscopy with unpolarised HeI, NeI and ArI radiations. Compared to pure Ag, the alloy spectra are found to be broadened and the main features slightly (0.1 eV) shifted to higher binding energy as a result of adding Mn into Ag. In addition, there is an increase in intensity between Fermi level and top of the Ag 4d-band and significant changes in thed-band region. However, a well-defined Mn spin-up feature clearly separated from the top of Ag 4d-band is not seen in the alloy photoemission spectra. It is suggested that this is due to the strong hybridisation between the Mnd-states and Agd- andsp-states. Our results do not support the virtual bound state model for Mn in Ag for concentration range5 at.% Mn.     

Electronic Structure of Nitrites of Metals

Within the framework of the theory of local electronic density functional, the band structure, the density of states, and the electronic density of MNO₂ (M: Na, K, Rb, Cs, Tl, and Ag) nitrites are calculated by the pseudopotential method in the basis of numerical sp ³ d ⁵ atomic pseudo-orbitals. The series dependence of the electronic structure parameters is examined, the role of metals in the energy band formation is established, and conclusions on the character of chemical bonds in these compounds are drawn.     

Intracenter transitions of iron-group ions in II–VI semiconductor matrices

A review is made of studies of intracenter optical transitions in 3d shells of iron-group divalent (magnetic) ions. Attention is focused on the emission spectra of Mn²⁺ ions in CdTe, ZnS, and ZnSe crystals. An analysis is made of the structure of intracenter absorption and luminescence and of the effect that the elemental matrix composition, magnetic-ion concentration, temperature, hydrostatic pressure, and structural phase transitions exert on the intracenter transitions. The mutual influence of two electronic excitation relaxation mechanisms, interband and intracenter, is considered. The specific features of the intracenter emission of magnetic ions embedded in two-dimensional systems and nanocrystals associated with a variation in sp-d exchange interaction and other factors are discussed. Data on the decay kinetics over the intracenter luminescence band profile are presented as a function of temperature, magnetic ion concentration, and excitation conditions. The saturation of the luminescence and the variation of its kinetic properties under strong optical excitation, which are caused by excitation migration and the cooperative effect, as well as the manifestation of a nonlinearity in intracenter absorption, are studied.     

Underestimating the width of the bandgap in the electronic spectra of La2CuO4

It is shown that the width of the bandgap determined by the simultaneous analysis of the experimental photoelectron and inverse photoemission spectra of the surface of La₂CuO₄ using a common energy scale is underestimated by 1 eV. The electronic and satellite structures of the spectra of La₂CuO₄ are calculated on the basis of the multiband p-d model and the sudden perturbation approximation. It is shown that shakedown processes shift the one-electron contour of the final two-hole configuration of the photoelectron spectrum 1 eV down the energy scale and shift the contour of the final d ¹⁰ configuration of the inverse photoemission spectrum downward by 2 eV; these shifts cause the energy splitting between the filled and empty bands to be underestimated. Fiz. Tverd. Tela (St. Petersburg) 39, 449–451 (March 1997)     

Effect of oxidation state and coordination with Hg(II) on the electronic spectra of an anthraquinone–rhodamine sensor

ABSTRACT

In this study, a computational examination of the electronic transitions and through-space energy transfer processes lends insight into the experimental electronic spectra of a redox-sensitive rhodamine–anthraquinone dyad. Electronic transitions were calculated using density functional theory (DFT) and time-dependent DFT (TDDFT) based on models optimised from single-crystal X-ray diffraction (XRD) ion positions. DFT calculations were performed on gas-phase models using the Vienna Ab Initio Software Package (VASP) with the functional developed by Perdew, Burke, and Ernzerhof (PBE) on a basis set of plane waves. Using the DFT results, select transitions were evaluated based on a dipole–dipole coupling mechanism to find the Förster resonance energy transfer coupling, the square of which is approximately proportional to the rate of energy transfer between the donor and the acceptor. Electronic transitions during the relaxation of charge carriers are also investigated using nonadiabatic molecular dynamics. In order to investigate the transitions contributing to key peaks in the experimental absorbance spectra, TDDFT calculations were performed in Gaussian 09 with the B3LYP functional on the sensor in solution phase, which is simulated using a polarisable continuum model (PCM). The computed electron transfer process from the excited rhodamine to the quinone correlates better with the experimental data than does the computed Förster resonance energy transfer (FRET) process. This computed electron transfer process is faster than the radiative lifetime of the fluorescent state, which collectively suggests that the charge transfer process quenches fluorescence. These results support the observation that fluorescence is more prominent in the oxidised sensor than in the reduced sensor.     

Transmission of electrons through ferromagnetic material and applications to detection of electron spin polarization

The salient features of the total low energy inelastic electron scattering cross section in transition metals are described by a constant term σ₀ plus a term σ_d that is proportional to the number of unoccupied d-orbitals. This simple model predicts that low energy electrons transmitted through a ferromagnetic ultrathin film acquire a transport spin polarization a(χ). Using the ratio σ₀/σ_d as the only adjustable parameter, the model predicts the enhancement of the spin polarization of the low energy cascade electrons as well as a(χ) in reasonable agreement with the existing observations on Fe, Co and Ni. A detector for electron spin polarization P based on the spin dependent transmission of electrons through ferromagnetic material is proposed which should be superior to existing P-detectors by 1–2 orders of magnitude.     

A vibronic-structure analysis of optical spectra in ZnO:Ni3+ crystals by localized-vibration simulation

A theoretical study is reported of the vibrations associated with a Ni³⁺ impurity charged with respect to the ZnO lattice. The calculations were made by a recursive method in terms of the shell model for vibrations with different symmetries. The vibronic structure observed in the spectra of d-d intracenter transitions in the Ni³⁺ impurity has been interpreted using model calculations. Fiz. Tverd. Tela (St. Petersburg) 41, 618–622 (April 1999)     

Electronic structure of prototype AFe<Subscript>2</Subscript>As<Subscript>2</Subscript> and ReOFeAs high-temperature superconductors: A comparison

We have performed ab initio LDA calculations of the electronic structure of newly discovered prototype high-temperature superconductors AFe₂As₂ (A = Ba, Sr) and compared it with the previously calculated electronic spectra of ReOFeAs (Re = La, Ce, Pr, Nd, Sm). In all cases, we obtain almost identical densities of states in a rather wide energy interval (up to 1 eV) around the Fermi level. Energy dispersions are also very similar and almost two dimensional in this energy interval, leading to the same basic (minimal) model of the electronic spectra, determined mainly by Fe d orbitals of the FeAs layers. The other constituents, such as A ions or rare-earth Re (or oxygen states) are more or less irrelevant for superconductivity. LDA Fermi surfaces for AFe₂As₂ are also very similar to that of ReOFeAs. This makes the more simple AFe₂As₂ a generic system to study the high-temperature superconductivity in FeAs-layered compounds. The text was submitted by the authors in English.     

NMR Studies of Hindered Rotation and Magnetic Anisotropy: The Diels–Alder Adducts of Phencyclone with N‐Phenylmaleimide and N‐(2‐Trifluoromethylphenyl)maleimide. Ab Initio Calculations for Optimized Structures

Abstract

N‐Phenylmaleimide, 2, and N‐(2‐trifluoromethylphenyl)maleimide, 3, were separately added to phencyclone, 1, to yield the corresponding phencyclone Diels–Alder adducts, 4 and 5. The resulting adducts (and some precursors) have been characterized by one‐ and two‐dimensional ¹H and ¹³C NMR at 300 and 75 MHz, and by ¹⁹F NMR at 282 MHz, at ambient temperatures. The NMR data are consistent, for both adducts, with: (a) hindered rotation of the bridgehead unsubstituted phenyl groups about the C(sp²)–C(sp³) bonds, based on slow exchange limit (SEL) spectra and (b) endo adduct configuration based on magnetic anisotropic effects in the ¹H NMR. The NMR spectra of the phencyclone adduct, 4, of N‐phenylmaleimide, indicate free rotation on the NMR timescales (fast exchange limit, FEL spectra) about the N‐phenyl bond. The spectra for the adduct, 5, of N‐(2‐trifluoromethylphenyl)maleimide are interpreted as consistent with SEL regimes, for the N‐aryl rotations, with a single rotamer present in which the trifluoromethyl group is directed “out of” the adduct cavity, and away from the phenanthrenoid moiety. This conclusion is based, in part, on NMR data suggesting the apparent slow N‐aryl bond rotation in a pair of atropisomers corresponding to the acetic acid addition products from the N‐(2‐trifluoromethylphenyl)maleimide. Evidence of magnetic anisotropic effects due to the phenanthrenoid moiety and proximal carbonyls is discussed. ¹H, ¹³C, and ¹⁹F assignments are presented and interpreted. Molecular modeling calculations at the Hartree–Fock level, 6‐31G* basis set, were performed to provide geometry optimizations for energy‐minimized structures of selected compounds.     

Electronic and spectral properties of ametal-organic super container molecule by single point DFT

ABSTRACT

Metal-organic super container (MOSC) molecules are ideal candidates for photocatalysis due to their construction with transition metal centres and tuneable cavity sizes that could house catalytic sites. The basic electronic structure for a model of extremely large size (more than 2000 ions) is explored by single point calculation using unrestricted density functional theory, and Perdue–Burke–Ernzerhof functional in Vienna ab initio simulation package software. The information obtained through these calculations (such as density of states, absorbance spectra, and charge density) will allow for analysis of a MOSC's catalytic ability. Electronic characteristics of the nanostructures (MOSCs and their building blocks) in the ground and photoexcited electronic configurations are examined. We explore if the presence of transition metal ions with open shells in such close proximity to one another may result in high spin configurations and show any arrangement into ferromagnetic ordering. Spin-unrestricted computation was applied to evaluate how optical properties could be affected by d–d transitions. A scan of a spin-polarisation parameter allows one to resolve spin configuration and obtain a connection between theory and experiment. Analysis of Kohn–Sham orbitals of interest provides insight into charge transfer mechanisms, which were found to contribute to multiple low-energy charge transfer states to the electronic structure.     

Symmetry aspect of the phase transitions in boracites

The phase transitions in boracites are analysed by using the group-theoretical formulation of the Landau theory of phase transitions. It is shown that the orthorhombic, monoclinic and trigonal phase transitions could be induced by the same irreducible representation of the space groupT _d ⁵ with the star determined by the wave vectork=1/2(b ₁+b ₂). The corresponding free energy function is constructed and the symmetry of normal modes is discussed.The authors thank Dr. V. Janovec of the Institute of Physics for valuable remarks to this paper.     

NIR-VIS reflectivity spectra of some transition metal thiophosphates

Summary Room temperature optical-reflectivity measurements on some transition metal thiophosphates were carried out in the near infrared and visible regions. The resulting spectra, interpreted on the basis of the ?transition metal weakly interacting? model, agree well with earlier optical transmission measurements. Below the fundamental absorption edge, the observed features have been assigned to 3d–3d transitions occurring on the transition metal ion, while those observed at photon energies greater than the absorption threshold have been attributed to transitions from the valence bands to discrete 3d orbital levels or to the conduction bands. A more detailed information on the metal ion 3d levels energy distribution with respect to the valence band states belonging to the (P₂S₆)^4- cluster and a more precise determination of the MPS₃ absorption edge energy position have been obtained.     

Electronic structure and X-ray spectra of transition metal sulfides NiS,CuS, and ZnS

A numerical electronic band structure calculations for sulfides NiS, CuS, and ZnS are carried out. Using the results a detailed analysis of a valence states is performed; obtained partial densities of states are compared with X-ray SL _2,3 and $ SK_{\beta _{1,3} } $ SK_{\beta _{1,3} } -emission spectra. We showed that spectrum lineshape depends on hybridization strength between various Me(3d)-orbitals and 3p-states of sulfur. The hybridization strength and the symmetry of hybrid Me(3d)-orbitals are defined by crystal lattice structure. Finally a well splitted in energy bonding and antibonding states Me(3d)-S(3p) appear while weakly hybridized Me(3d)-states mainly contribute to spectra intensity in the energy between them. A good agreement between the theoretical and the experimental spectra of valence band for considered sulfides is obtained.     

Half-metallicity in Rh-doped TiO<Subscript>2</Subscript> from ab initio calculations

First-principles calculations based on density functional theory (DFT) are performed to study the electronic structures and magnetic properties of Rh-doped TiO₂ crystals. The hybridization between Rh-4d and O-2p results in Rh becoming ferromagnetic with a magnetic moment of about 1.0 μ _B per supercell. The Rh-doped TiO₂ system exhibits half-metallic ferromagnetism based both DFT and DFT + U. The strong ferromagnetic couplings between local magnetic moments can be attributed to both the p-d hybridization and double-exchange mechanisms, as well as superexchange interaction. These results suggest an alternative approach to achieve promising dilute magnetic semiconductors by doping non-magnetic transition metals in a TiO₂ host.     

Physical mechanism of swift heavy ion irradiation effect in graphene

ABSTRACT

The damage production induced by swift heavy ion irradiation in single-layer graphene (SLG) is investigated by molecular dynamics method. By given energy to a cylindrical region, the latent track consisting of nanopore and non-six-member rings can be produced, which depends on the electronic energy loss (dE/dx). For SLG, the minimum value needed to generate defects lies in 6.5–10?keV/nm. The latent track formation begins with the decomposition of the structure in energy deposition region until the atomic fragments escape from the surface and gradually decompose into atomic clusters. At the same time, the structure of system also changes. The source power of this phenomena is the accumulation and outward propagation of atomic stress in energy deposition region.     

Heating of magnons by hot charge carriers and electrical properties of HgCr2Se4

Strong variations of the conductivity and the Hall coefficient as a function of the magnetic and electric field strengths are discovered in the ferromagnetic semiconductor HgCr₂Se₄. The nature of these phenomena is discussed in connection with its electronic structure and the strong interaction between the electric and magnetic subsystems in this magnetic semiconductor. The results can be interpreted within a model of ordinary semiconductors with consideration of the strong electron-magnon interaction specific to magnetic semiconductors, the heating of magnons by hot charge carriers, and the trapping of charge carriers (the formation of ferrons) due to the s-d exchange interaction. Fiz. Tverd. Tela (St. Petersburg) 39, 664–667 (April 1997)