Electronic structure and magnetic coupling in CaV<Subscript>2</Subscript>O<Subscript>5</Subscript>: spin dimer versus spin ladder

The electronic structure and magnetic exchange interactions of the ladder vanadate CaV₂O₅ have been studied by ab initio electronic structure calculations based on density functional theory (DFT). Geometry optimization and electronic structure calculations are performed using spin-polarized generalized gradient approximation (GGA) exchange-correlation functionals for four possible spin-ordered states. The experimentally observed insulating behavior has been reproduced successfully in the framework of the band theory by considering the magnetic ordering. Calculated results reveal that the true magnetic ground state of CaV₂O₅ is the antiferromagnetic (AFM) state with AFM exchange interactions both inside the rungs and along the ladder legs. Calculated exchange parameters indicate that the ladder structural vanadate CaV₂O₅ should be described as weakly coupled dimer system rather than as spin ladder compound. The AFM interactions inside the dimer are crucial to the insulating ground state and magnetic characteristics of CaV₂O₅.     

Theoretical studies on the electronic structure and magnetic properties of Cu(2,5-dmpz)Cl2

First-principles calculations have been performed to study the electronic structure, the metallic and magnetic properties of Cu(2,5-dmpz)Cl₂. The calculations are based on the density functional theory (DFT) with the generalized gradient approximation (GGA) and the full-potential-linearized-augmented plane wave (FPLAPW) method. The total energy, magnetic moment, density of states (DOS) and electronic band structure are calculated. The results reveal that the compound has a stable semiconductive antiferromagnetic (AFM) ground state and a semiconductive ferromagnetic (FM) metastable state, which is in good agreement with the experimental results. Based on the spin distribution and the DOS, it is found that the spin magnetic moment is mainly from the Cu²⁺, and with relative small contribution from Cl, N atoms.     

The electronic structure and magnetic properties of metallic antiferromagnetic Co[(CH3PO3)(H2O)] studied by first-principles calculations

The electronic structure, the metallic and magnetic properties of metal phosphonate Co[(CH₃PO₃)(H₂O)] have been studied by first-principles calculations, which were based on the density-functional theory (DFT) and the full potential linearized augmented plane wave (FPLAPW) method. The total energy, the spin magnetic moments and the density of the states (DOS) were all calculated. The calculations reveal that the compound Co[(CH₃PO₃)(H₂O)] has a stable metallic antiferromagnetic (AFM) ground state and a half-metallic ferromagnetic (FM) metastable state. Based on the spin distribution obtained from calculations, it is found that the spin magnetic moment of the compound is mainly from the Co²⁺, with some small contributions from the oxygen, carbon and phosphorus atoms, and the spin magnetic moment per molecule is 5.000μ_B, which is in good agreement with the experimental results.     

Half-metallic ferromagnetism in cubic perovskite type NdInO3

ABSTRACT

Based on the full-potential linearised augmented plane wave plus local orbitals (FP-L/APW?+?lo) method within the density functional theory (DFT), the structural, electronic, and magnetic calculations of the cubic oxide perovskite NdInO₃ compound have been done under the generalised gradient approximation (GGA). The exchange and correlation (XC) potential is defined as GGA framework in the analyses of structural properties, while both GGA and GGA?+?U (U is the Hubbard correlation term) approximations are taken to treat the electronic and magnetic properties. It is found that ferromagnetic (FM) configuration is reported as the most stable ground state of the cubic NdInO₃ material; however, the equilibrium lattice parameters such as lattice constant (a₀ ), bulk modulus (B₀ ), its first-pressure derivative (B’), and the minimum of total energy (E₀ ) are given in paramagnetic (PM), ferromagnetic (FM), and anti-ferromagnetic (AFM) states. The spin-polarized electronic structure calculations (band structure and density of states) of the cubic oxide perovskite NdInO₃ compound verify the half-metallic feature due to the spin-up case which has the metallic nature, whereas the spin-down case presents the semiconducting character. Moreover, the magnetic properties show the integer value of the total magnetic moment for the studied compound (3μ_B ), where it is manly contributed by Nd atoms with apparition of weak local magnetic moments in non magnetic In and O sites.     

梯形化合物NaV2O4F电子结构的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理赝势平面波方法, 通过自旋极化的广义梯度近似(GGA)电子结构计算对梯形化合物NaV₂O₄F进行了研究. 考虑了四种假想的自旋有序态,计算结果表明该化合物的磁基态具有二维反铁磁(AFM)结构, 即沿梯阶和梯腿方向都表现为AFM作用. 能带结构显示NaV₂O₄F为绝缘体材料, 带隙约为1.0eV. 方锥体中的晶体场劈裂使得VO₄F方锥体中的 V^{4+ 关键词： 2O₄F')" href="#">NaV₂O₄F 梯形化合物 第一性原理计算 电子结构}     

Phase stability,electronic, magnetic and elastic properties of Ni2CoZ(Z = Ga,Sn): A first principles study with GGA method and GGA+U approach

First principles calculations based on density functional theory are used to investigate the phase stability, electronic, magnetic and elastic properties of ferromagnetic metallic full-Heusler Ni₂CoZ(Z = Ga, Sn) alloys via the FP-LAPW method by the generalized gradient GGA and GGA+U approximations for the exchange and correlation energy, within the Perdew–Burke–Ernzerhof (PBE 96) parameterization. The results of calculating electronic structures and magnetic properties reveal that the both Ni₂CoGa and Ni₂CoSn crystallize in L2₁ phase with regular cubic structure. The two investigated compounds exhibit metallic ferromagnetic behaviors for the GGA+U calculation. The computation of elastic constants with GGA+U approach shows that our compounds are mechanically stable.     

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.     

Multiresolution quantum chemistry in multiwavelet bases: time-dependent density functional theory with asymptotically corrected potentials in local density and generalized gradient approximations

A multiresolution solver for fully numerical linear response calculations of excitation states via the time-dependent Hartree–Fock and density functional theory (TD-HF/DFT) is presented. The linear response method Yanai et al. previously reported [J. Chem. Phys., submitted] was limited to the Tamm–Dancoff approximation and could only use the Hartree–Fock exchange and the local-spin density approximation (LSDA) with a crude asymptotic correction. The present development enables us to perform full TD-HF/DFT calculations employing generalized gradient approximation (GGA) exchange-correlation potentials as well as hybrid ones. The linear response of TD-HF/DFT is computed by means of iteratively solving the coupled integral equations with the Green's functions. In this study, Tozer and Handy's asymptotic correction (AC) is applied to existing DFT exchange-correlations, and is found numerically stable and efficient. Furthermore, the new hybrid exchange-correlation functional CAM-B3LYP, which was recently proposed by Yanai et al. [Chem. Phys. Lett. 393, 51 (2004)], is implemented. The implementation requires a new separated representation of the integral kernel for the Coulomb-attenuated potential. We demonstrate linear response calculations free of basis set error for the excited states of Be, N₂, C₂H₄ and C₆H₆ using LSDA, HCTH, CAM-B3LYP and PBE0 exchange-correlation functionals. The mean absolute errors of the C₆H₆ calculations with HCTH and CAM-B3LYP are 0.12 and 0.18?eV, respectively. The second derivative of exchange-correlation functionals is represented fully numerically at O(N) computation cost.     

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.     

Photoinduced dynamics to photoluminescence in Ln3+ (Ln = Ce,Pr) doped β-NaYF4 nanocrystals computed in basis of non-collinear spin DFT with spin-orbit coupling

ABSTRACT

In this work, non-collinear spin DFT + U approaches with spin-orbit coupling (SOC) are applied to Ln³⁺ doped β-NaYF₄ (Ln = Ce, Pr) nanocrystals in Vienna ab initio Simulation Package taking into account unpaired spin configurations using the Perdew–Burke–Ernzerhof functional in a plane wave basis set. The calculated absorption spectra from non-collinear spin DFT + U approaches are compared with that from spin-polarised DFT + U approaches. The spectral difference indicates the importance of spin–flip transitions of Ln³⁺ ions. Suite of codes for nonadiabatic dynamics has been developed for 2-component spinor orbitals. On-the-fly nonadiabatic coupling calculations provide transition probabilities facilitated by nuclear motion. Relaxation rates of electrons and holes are calculated using Redfield theory in the reduced density matrix formalism cast in the basis of non-collinear spin DFT + U with SOC. The emission spectra are calculated using the time-integrated method along the excited state trajectories based on nonadiabatic couplings.     

阻挫三角反铁磁AgCrO2螺旋自旋序的第一性原理研究

基于密度泛函理论的广义梯度近似(GGA)和投影缀加波(PAW)方法,分别从共线和非共线磁性结构出发,研究了自旋阻挫三角反铁磁AgCrO₂的基态、磁性以及电子结构,从理论计算的角度给出了基态磁性结构.计算结果表明:AgCrO₂具有120°螺旋自旋序反铁磁基态,其自旋螺旋面平行于(110)面或(11^-0)面;由于Cr离子间的自旋几何阻挫,导致沿晶体的a,b和a+b方向上均形成了螺旋自旋转动角为120°的 关键词： 第一性原理 交换相互作用 阻挫 反铁磁     

Exchange Bias in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite

It is established that excess oxygen content δ influences the exchange bias (EB) in layered GdBa-Co₂O_{5 + δ} cobaltite. The EB effect arises in p-type (δ > 0.5) cobaltite and disappears in n-type (δ < 0.5) cobaltite. The main parameters of EB in GdBaCo₂O_5.52(2) polycrystals are determined, including the field and temperature dependences of EB field H _EB , blocking temperature T _B , exchange coupling energy J _i of antiferromagnet–ferromagnet (AFM–FM) interface, and dimensions of FM clusters. The training effect inherent in systems with EB has been studied. The results are explained in terms of exchange interaction between the FM and AFM phases. It is assumed that the EB originates from the coexistence of Co³⁺ and Co⁴⁺ ions that leads to the formation of monodomain FM clusters in the AFM matrix of cobaltite.     

A study on defect formation and magnetic properties of nitrogen-doped ZnO nanowires by the first principles

Theoretical calculation based on density functional theory (DFT) and generalized gradient approximation (GGA) has been carried out in studying defect formation energies, ionizing energies and ferromagnetism of nitrogen-doped ZnO nanowires. The result shows that N_O is deep acceptor, which make it hard to ionize. Ferromagnetic (FM) and antiferromagnetic (AFM) coupling between N atoms are also investigated. The results show that FM coupling between N atoms is more stable than AFM coupling. The FM coupling mechanism is explained by the interaction of N energy level. In addition, zinc and oxygen vacancies affecting FM coupling is also discussed. It is found that zinc and oxygen vacancies are unfavorable for stabilizing FM coupling of nitrogen-doped ZnO nanowires.     

First-principle study of full Heusler Co2Y Si using PBE0 hybrid functional

First-principle self-consistent full potential linear augmented plane wave calculations based on density functional theory using hybrid functional PBE0 are performed to study magnetic moments, density of states and half-metallicity of L2₁ type full Heusler alloys with formula Co₂Y Si. Y is Ti, V, Mn and Fe. We have compared these results with those of the PBE-GGA exchange correlation functional and the LDA + U method. The results for Co₂FeSi and Co₂MnSi are completely different; using the PBE0 hybrid functional for Co₂FeSi predicts experimental magnetic moment and also predicts this material to be half-metallic ferromagnet, while using PBE-GGA predicts it not to be half-metal. The results of PBE0 are more similar to the ones obtained by LDA + U method.     

Spin-polarized calculations of electronic structures in ferromagnetic and antiferromagnetic Zn0.75TM0.25Se (TM=Cr,Fe, Co and Ni)

In this work, we aim to examine the spin-polarized electronic band structures, the local densities of states as well as the magnetism of Zn_1−xTM_xSe (TM=Cr, Fe, Co and Ni) diluted magnetic semiconductors in the ferromagnetic (FM) and antiferromagnetic (AFM) phases, and with 25% of TM. The calculations are performed by the developed full-potential augmented plane wave plus local orbitals method within the spin density functional theory. As exchange-correlation potential we used the generalized gradient approximation (GGA) form. We treated the ferromagnetic and antiferromagnetic phases and we found that all compounds are stable in the ferromagnetic structure. Structural properties are computed after total energy minimization. Our results show that the cohesive energies of Zn_0.75TM_0.25Se are greater than that of zinc blende ZnSe. We discuss the electronic structures, total and partial densities of states, local moments and the p–d exchange splitting. Furthermore, we found that p–d hybridization reduces the local magnetic moment of TM and produces small local magnetic moments on the nonmagnetic Zn and Se sites. We found also that in the AFM phase the TM local magnetic moments are smaller than in the FM phase; this is due to the greater interaction of the TM d-up and d-down orbitals.     

An ab initio study of PuO<Subscript>2±0.25</Subscript>, UO<Subscript>2±0.25</Subscript>, and U<Subscript>0.5</Subscript>Pu<Subscript>0.5</Subscript>O<Subscript>2±0.25</Subscript>

Hybrid density functional theory has been used to systematically study the electronic, geometric, and magnetic properties of strongly correlated materials PuO_2±x , UO_2±x , and U_0.5Pu_0.5O_2±x with x = 0.25. The calculations have been performed using the all-electron full- potential linearized augmented plane wave plus local orbitals basis (FP-L/APW+lo) method. Each compound has been studied at the ferromagnetic (FM) and anti-ferromagnetic (AFM) configurations with and without spin-orbit coupling (SOC) and full geometry optimizations. The optimized lattice constants, bulk moduli, and band gaps are reported. Total energy calculations indicate that the ground states are AFM for all compounds studied here and the band gaps are typically higher than 1.0 eV, characteristic of semiconductors. The total energy is lowered significantly and the band gaps increase with the inclusion of SOC. The chemical bonds between the actinide metals and oxygen atoms are primarily ionic in character.     

First-principles studies of magnetic properties and electronic structure of EuC60

The full potential linearized augmented plane wave (FP-LAPW) method with the GGA+U approach was applied to study the electronic structures of the compound Eu₆C₆₀. Present calculations show that the hybridization between the Eu s, d state and the C₆₀ π states plays an essential role in its FM exchange interactions between the 4f electrons and metallic properties.