A comparative study of a Heusler alloy Co2FeGe using LSDA and LSDA+U

We have calculated the on-site Coulomb repulsion (U) for the transition elements Co and Fe. To study the impact of Hubbard potential or on-site Coulomb repulsion (U) on structural and electronic properties the calculated values of U were added on GGA and LSDA. We performed the structure optimization of Co₂FeGe based on the generalized gradient approximation (GGA and GGA+U). The calculation of electronic structure was based on the full potential linear augmented plane wave (FP-LAPW) method and local spin density approximation (LSDA) as well as exchange correlation LSDA+U. The Heusler alloy Co₂FeGe fails to give the half-metallic ferromagnetism (HMF) when treated with LSDA. The LSDA+U gives a good result to prove that Co₂FeGe is a HMF with a large gap of 1.10 eV and the Fermi energy (E_F) lies at the middle of the gap of minority spin. The calculated density of states (DOS) and band structure show that Co₂FeGe is a HMF when treated with LSDA+U.     

Study on the ground state of NiO: The LSDA (GGA)+U method

The ground-state properties of NiO have been investigated using the all-electron full-potential linearized augmented plane wave (FLAPW) and the so-called LSDA (GGA)+U (LSDA—local-spin-density approximation; GGA—generalized gradient approximation) method. The calculated result indicates that our estimation of U is in good agreement with experimental data. It is also found that none of the LSDA (GGA) methods is able to provide, at the same time, accurate electronic and structural properties of NiO. Although the GGA+U method can properly predict the electronic band gap, it overestimates the lattice constant and underestimates the bulk modulus. Then only the LSDA+U method accurately reports the electronic and structural properties of NiO. The calculated band gap and the density of states (DOS) show that the material NiO is the charge-transfer insulator, which agrees with the spectroscopy data. The comparison between the charge density of LSDA (not considering U) and that of LSDA+U (considering U) demonstrates that the trend of ionic crystal for NiO is obvious.     

Electronic structure of YMn2O5 studied by EELS and first-principles calculations

The electronic structure of multiferroic YMn₂O₅ material has been studied by use of the generalized gradient approximation (GGA). The results demonstrate that the oxygen 2p and manganese 3d orbitals are strongly hybridized. Considering the on-site Coulomb interaction U, we performed the GGA+U calculations for 0 < U ? 8 eV, and it is found that the increase of U could enlarge the band gap and, on the other hand, weaken the Mn-O hybridization. The experimental measurements of the electron energy-loss spectrometry (EELS) exhibit a rich variety of structural features in both O-K edge and Mn-L edges. A theoretical and experimental analysis on the O-K edge suggests that the on-site Coulomb interaction (U) in YMn₂ O₅ could be less than 4 eV. Certain electronic structural features of LaMn₂O₅ have been discussed in comparison with those of YMn₂O₅.     

A DFT + U description of oxygen vacancies at the TiO2 rutile (1 1 0) surface

Experimental observations indicate that removing bridging oxygen atoms from the TiO₂ rutile (1 1 0) surface produces a localised state approximately 0.7 eV below the conduction band. The corresponding excess electron density is thought to localise on the pair of Ti atoms neighbouring the vacancy; formally giving two Ti³⁺ sites. We consider the electronic structure and geometry of the oxygen deficient TiO₂ rutile (1 1 0) surface using both gradient-corrected density functional theory (GGA DFT) and DFT corrected for on-site Coulomb interactions (GGA + U) to allow a direct comparison of the two methods. We show that GGA fails to predict the experimentally observed electronic structure, in agreement with previous uncorrected DFT calculations on this system. Introducing the +U term encourages localisation of the excess electronic charge, with the qualitative distribution depending on the value of U. For low values of U (?4.0 eV) the charge localises in the sub-surface layers occupied in the GGA solution at arbitrary Ti sites, whereas higher values of U (?4.2 eV) predict strong localisation with the excess electronic charge mainly on the two Ti atoms neighbouring the vacancy. The precise charge distribution for these larger U values is found to differ from that predicted by previous hybrid-DFT calculations.     

A full potential all-electron calculation on electronic structure of NiO

We perform a first principle calculation on NiO system, a prototypical correlated electronic system due to partial filled 3d electronic shell, using various density functional theory (DFT) and hybrid functional methods inclusion of spin polarization (SP), on-site Coulomb repulsion U and spin–orbit coupling (SOC) effects. It is shown that localized spin density approximation (LSDA) plus U (LSDA?+?U) correctly reproduce experimental lattice parameter, while spin polarization generalized gradient approximation (SP?+?GGA?+?U) obviously overestimates lattice parameter. LSDA?+?U/SP?+?GGA?+?U band gaps and magnetic moments are in agreement with experimental data, and correctly predict NiO to be an insulator. NiO undergoes a Mott–Hubbard metal–insulator transition (MIT) by addition of Coulomb interaction U. Our LSDA?+?SOC calculation shows that SOC further splitting of Ni d e_g and t_2g orbitals into d_z2, d_xy, d_x2y2 and d_xz?+?d_yz orbitals, and SP nearly cancels out SOC effect, giving rise to symmetry of density of states (DOS) for spin-up and spin-down states, hence appearance of zero net magnetic moment. For LSDA?+?U?+?SOC calculation, combination effect of SP, U and SOC results in non-occupying of spin-up conduction band and a negligible density of states for spin-down states.     

A better ferrimagnetic half-metal LuCu3Mn4O12: Predicted from first-principles investigation

Electronic structure calculations based on density functional theory (DFT) within the generalized gradient approximation (GGA) and GGA+U for manganite cuprate compound LuCu₃Mn₄O₁₂ have been performed, using the full-potential linearized augmented plane wave method. The calculated results indicate that LuCu₃Mn₄O₁₂ is ferrimagnetic and half-metallic in both GGA and GGA+U calculations. The minority-spin band gap is 0.7 eV within GGA, which is larger than that of LaCu₃Mn₄O₁₂ (0.3 eV), indicating its better half-metallicity. Further, the minority-spin gap enlarges from 0.7 to 2.8 eV with U taken into account, and simultaneously the Fermi level being shifted to the middle of the gap, making the half-metallic energy gap to be 1.21 eV. These results demonstrate that electronic correlation effect enhances the stability of half-metallic property. These facts make this system interesting candidates for applications in spintronic devices.     

Role of Coulomb interactions in semicore levels Ga d levels of GaX semiconductors: Implication on band offsets

The positions of the semicore Ga d levels in GaX semiconductors (X=N,P, and As) are underestimated in density functional calculations using either the local density approximation LDA or the generalized gradient approximation GGA for the exchange functional. Correcting for this inaccuracy within LDA+U calculations with an on-site Coulumb interaction U on the semicore d-states results in a modest enhancement of the band gap. We show that this modest enhancement of the band-gap energy comes from the movement of the valence-band maximum alone, thus not affecting the conduction-band states. Further, the localization of the charge on Ga d states with U leads to a regulation of charge on Ga. This yields a shift of 1–2 eV of the core levels on the Ga atom while the anion core levels remain unchanged.     

The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

The electronic structure and ferromagnetic stability of Co-doped SnO₂ are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U_Co transforms the ground state of Co-doped SnO₂ to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U_Co calculations show that the pure substitutional Co defects in SnO₂ cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U_Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U_Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U_O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U_Co calculations are not changed by the correction of band gap.     

First-principles investigation of the electronic structure and magnetism of eskolaite

The electronic structure and magnetism of eskolaite are studied by using first-principles calculations where the on-site Coulomb interaction and the exchange interaction are taken into account and the LSDA+U method is used. The calculated energies of magnetic configurations are very well fitted by the Heisenberg Hamiltonian with interactions in five neighbour shells; interaction with two nearest neighbours is found to be dominant. The Néel temperature is calculated in the spin-3/2 pair-cluster approximation. It is found that the measurements are in good agreement with the calculations of lattice parameters, density of states, band gap, local magnetic moment, and the Néel temperature for the values of U and J that are close to those obtained within the constrained occupation method. The band gap is of the Mott--Hubbard type.     

Antiferromagnetism of perovskite EuZrO3 from a first-principles study

Electronic structure and magnetic properties of perovskite EuZrO₃ have been investigated using the ab initio density-functional calculations with local spin density approximation (LSDA) and LSDA+U methods. The results that are obtained reveal that the antiferromagnetic G-type arrangement is more stable than other possible configurations. The ground G-AFM state shows the insulator property with an energy gap of about 0.27 eV at U=0 eV. It is found that the energy gap strongly depends on the correction potential parameter of U due to the strong interaction of the f electrons of Eu in EuZrO₃. The spin magnetic moment of Eu ions is predited to be 6.82μ_B, which is in well agreement with the experimental result of 6.87μ_B.     

First-principles linear muffin-tin orbital investigations in the electronic and magnetic structures of double perovskites Ba2TMoO6 (T=V,Cr, Mn,Fe and Co)

The electronic and magnetic structures of ordered double perovskites Ba₂TMoO₆ (T=V, Cr, Mn, Fe and Co) are systematically investigated by means of the first-principle linear muffin-tin orbitals with the atomic-sphere approximation (LMTO-ASA) method. The calculations are performed by using the both local spin density approximation (LSDA) and the LSDA+U Coulomb interaction schemes. The results show a half-metallic ferrimagnetic ground states for T=Cr, Fe and Co in LSDA+U treatment, whereas half-metallic ferromagnetic character is observed for T=V. For T=Mn, insulating ground state is obtained, stabilized in the antiferromagnetic state. The LSDA+U calculations yield better agreement with the theoretical and the experimental results than do the LSDA.     

后钙钛矿CaRhO3的电子结构和磁学性质的第一性原理研究

采用基于密度泛函理论的投影平面波方法,对后钙钛矿结构(Ppv)的CaRhO₃的电子结构和磁学性质进行了研究.广义梯度(GGA)近似下的计算表明,Ppv-CaRhO₃的基态为铁磁性半金属,Rh⁴⁺离子的磁矩大小为0.57μ_B,具有低自旋态构型;而考虑在位库仑作用修正的GGA+U计算,得到了与实验结果相符的反铁磁绝缘体基态,表明后钙钛矿结构中4d电子之间的关联效应对体 关键词： 电子结构 磁学性质 金属绝缘体转变     

Ab initio study of the structural,electronic, elastic and magnetic properties of Cu2GdIn,Ag2GdIn and Au2GdIn

We preformed first-principle calculations for the structural, electronic, elastic and magnetic properties of Cu₂GdIn, Ag₂GdIn and Au₂GdIn using the full-potential linearized augmented plane wave (FP-LAPW) scheme within the generalized gradient approximation by Wu and Cohen (GGA-WC), GGA+U, the local spin density approximation (LSDA) and LSDA+U. The lattice parameters, the bulk modulus and its pressure derivative and the elastic constants were determined. Also, we present the band structures and the densities of states. The electronic structures of the ferromagnetic configuration for Heusler compounds (X₂GdIn) have a metallic character. The magnetic moments were mostly contributed by the rare-earth Gd 4f ion.     

Vacancy induced magnetism in SrTiO3

Vacancy-induced magnetism in perovskite SrTiO₃ is investigated by ab initio calculations and magnetic measurements. The calculations of the generalized gradient approximation (GGA), the local density approximation (LDA) and the local density approximation with on-site effect U (LDA+U) methods show that stoichiometric SrTiO₃ is nonmagnetic. The GGA calculated results indicate that Ti or O vacancy could induce magnetism rather than Sr vacancy. The LDA and LDA+U calculations show that the Ti vacancy could induce magnetism, while Sr and O vacancies couldn't. The experimental results confirm that SrTiO₃ nanocrystalline powders exhibit room-temperature ferromagnetism (FM) and the magnetic moment results from cation vacancies.     

Comparison of the structural and magnetic properties of ground-state SrTcO3 and CaTcO3 from first principles

The generalized gradient approximation (GGA) plus on-site Coulomb interaction corrections (GGA+U) method is employed for the total energies and electronic structure calculations of SrTcO₃ and CaTcO₃. G-type antiferromagnetic (G-AFM) is found to be ground state for both compounds, in consistence with the previous experimental results. The mechanism of Neel temperature of SrTcO₃ being higher than that of CaTcO₃ is explored. The insulating band gaps of SrTcO₃ and CaTcO₃ are found to be 1.71 eV and 1.74 eV, respectively. The magnetic moment of Tc1 is found to be 2.237μ_B in SrTcO₃ unit cell and 2.266μ_B in CaTcO₃ unit cell. Structural parameters and electronic structure of the two compounds are examined to explore the origin of their different electrical and magnetic characters.     

Electronic structures and mechanical properties of uranium monocarbide from first-principles and calculations

The electronic structure, elastic constants, Poisson's ratio, and phonon dispersion curves of UC have been systematically investigated from the first-principles calculations by the projector-augmented-wave (PAW) method. In order to describe precisely the strong on-site Coulomb repulsion among the localized U 5f electrons, we adopt the local density approximation (LDA)+U and generalized gradient approximation (GGA)+U formalisms for the exchange correlation term. We systematically study how the electronic properties and elastic constants of UC are affected by the different choice of U as well as the exchange-correlation potential. We show that by choosing an appropriate Hubbard U parameter within the GGA+U approach, most of our calculated results are in good agreement with the experimental data. Therefore, the results obtained by the GGA+U with effective Hubbard parameter U chosen around 3 eV for UC are considered to be reasonable.     

The importance of electron correlation in graphene and hydrogenated graphene

Local density approximation (LDA) and Green function effective Coulomb (GW) calculations are performed to investigate the effect of electronic correlations on the electronic properties of both graphene and graphane. The size of band gap in graphane increases from 3.7 eV in LDA to 4.9 eV in GW approximation. By calculating maximally localized Wannier wave functions, we evaluate the necessary integrals to get the Hubbard U and the exchange J interaction from first principles for both graphene and graphane. Our ab-initio estimates indicate that in the case of graphene, in addition to the hopping amplitude t ～ 2.8 eV giving rise to the Dirac nature of low lying excitations, the Hubbard U value of ～8.7 eV gives rise to a super-exchange strength of J _AFM ～ 3.5 eV. This value dominates over the direct (ferromagnetic) exchange value of J _FM ～ 1.6 eV. This brings substantial Mott-Heisenberg aspects into the problem of graphene. Moreover, similarly large values of the Hubbard and super-exchange strength in graphane suggests that the nature of gap in graphane has substantial Mott character.     

Optical spectroscopy and electronic structure of the Er5Ge3 compound

The results of the study of the optical properties and electronic structure of the Er₅Ge₃ compound have been presented. In the wavelength range of 0.22–15 μm (0.083–5.64 eV), the optical constants have been measured, and the spectral and electronic characteristics have been determined. The spin-polarization calculations of the band spectrum have been performed in the local electron spin density approximation (LSDA) with a correction for strong correlations in the 4f shell of the rare-earth atom (LSDA + U method). The main features of the experimental dispersion dependence of the optical conductivity in the region of quantum light absorption have been interpreted based on the results of calculations of the electron density of states.     

Magnetic and electronic structure studies of the perovskite oxide Nd2/3Sr1/3MnO3 from the first principle calculation

Generalized gradient approximation (GGA) and GGA + U (U denotes on-site Coulomb interactions) methods are applied to investigate the magnetic and electronic structures of the perovskite oxide Nd_2/3Sr_1/3MnO₃. Under GGA the compound prefers ferrimagnetic ordering in which Nd sublattice is spin-antiparallel to Mn sublattice. Nd 4f states cross over the Fermi level under GGA, leading the ferrimagnetic Nd_2/3Sr_1/3MnO₃ to a metallic character. The on-site Coulomb interactions should be included to emphasize the localized feature of Nd 4f states. Under GGA + U, the spins of Nd and Mn sublattices tend to be parallel in the ground state, and fully spin-polarized Mn 3d electrons yield a half-metallic band structure for the ferromagnetic Nd_2/3Sr_1/3MnO₃. The ferromagnetic coupling between Nd and Mn sublattices is ascribed to the super-exchange interaction between Nd 4f and Mn 3d (t2g) electrons via O 2p electrons.