Ground state valency and spin configuration of the Ni ions in nickelates

The ab initio self-interaction-corrected local-spin-density approximation is used to study the electronic structure of both stoichiometric and nonstoichiometric nickelates. From total energy considerations it emerges that, in their ground state, both LiNiO2 and NaNiO2 are insulators, with the Ni ion in the Ni3+ low-spin state (t(2g)(6)e(g)(1)) configuration. It is established that a substitution of a number of Li/Na atoms by divalent impurities drives an equivalent number of Ni ions in the NiO2 layers from the Jahn-Teller (JT)-active trivalent low-spin state to the JT-inactive divalent state. We describe how the observed considerable differences between LiNiO2 and NaNiO2 can be explained through the creation of Ni2+ impurities in LiNiO2. The indications are that the random distribution of the Ni2+ impurities might be responsible for the destruction of the long-range orbital ordering in LiNiO2.     

Electronic and magnetic properties of SiC nanoribbons by F termination

By using the first-principles calculations, the electronic properties are studied for the F-terminated SiC nanoribbons (SiCNRs) with either zigzag edges (ZSiCNRs) or armchair edges (ASiCNRs). The results show that the broader F-terminated ZSiCNRs are metallic and the edge states appear at the Fermi level, while the F-terminated ASiCNRs are always semiconductors independent of their width but the edge states do not appear due to the Si-C dimer bonds at the edges. The charge density contours analyses shows that the Si-F and Si-C bonds are all ionic bonds due to the much stronger electronegativities of the F and C atoms than that of the Si atom. However, the C-F bonds display a typical non-polar covalent bonding feature because of the electronegativity difference between the F and C atoms of 1.5 is a much smaller than that of between the F and Si atoms of 2.2, as well as the tighter bounded C 2s ²2p ² electrons with smaller orbital radius than the Si 3s ²3p ² electrons. For both the F- and the H-terminated ZSiCNRs, the ground state is a ferromagnetic semiconductor.     

激发态下甘氨酸与水分子间氢键性质研究

在生物体中氨基酸通常以水作为溶剂,是形成细胞的重要成分.在该环境下,分子间氢键的产生会对氨基酸分子与水分子的结构和性质产生影响.为了研究其在基态和激发态下的性质,本文利用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对甘氨酸分子和H₂O分子在基态和激发态下的分子间氢键的静电势、键长、自然键轨道(NBO)电荷、分子中的原子理论(AIM)分析、Wiberg键级b、红外(IR)光谱、空穴-电子轨道和基态与激发态之间的电子转移进行了理论研究.结果表明：分子间氢键的形成会导致分子结构的改变和红外光谱振动频率的移动.在激发态下,分子间氢键有不同程度的增强或减弱.该计算结果为氢键的形成和激发态下分子间氢键的研究提供理论依据.     

Orbital ordering and frustration of p-band Mott insulators

We investigate the general structure of orbital exchange physics in Mott-insulating states of p-orbital systems in optical lattices. Orbital orders occur in both the triangular and kagome lattices. In contrast, orbital exchange in the honeycomb lattice is frustrated as described by a novel quantum 120 degrees model. Its classical ground states are mapped into configurations of the fully packed loop model with an extra U(1) rotation degree of freedom. Quantum orbital fluctuations select a six-site plaquette ground state ordering pattern in the semiclassical limit from the "order from disorder" mechanism. This effect arises from the appearance of a zero energy flat band of orbital excitations.     

Orbital order in Mott insulators of spinless p-band fermions

A gas of strongly interacting single-species (spinless) p-orbital fermionic atoms in 2D optical lattices is proposed and studied. Several interesting new features are found. In the Mott limit on a square lattice, the gas is found to be described effectively by an orbital exchange Hamiltonian equivalent to a pseudospin-1/2 XXZ model. For a triangular, honeycomb, or kagome lattice, the orbital exchange is geometrically frustrated and described by a new quantum 120 degrees model. We determine the orbital ordering on the kagome lattice, and show how orbital wave fluctuations select ground states via the order by disorder mechanism for the honeycomb lattice. We discuss experimental signatures of various orbital ordering.     

Strong anisotropy of superexchange in the copper-oxygen chains of La(14)-xCaxCu24O41

Electron spin resonance data of Cu2+ ions in La(14)-xCaxCu24O41 single crystals (x = 9,11,12) reveal a very large width of the resonance line in the paramagnetic state. This signals an unusually strong anisotropy of approximately 10% of the isotropic Heisenberg superexchange in the Cu-O chains of this compound. The strong anisotropy can be explained by the specific geometry of two symmetrical 90 degrees Cu-O-Cu bonds, which boosts the importance of orbital degrees of freedom. Our data show the apparent limitations of the applicability of an isotropic Heisenberg model to the low-dimensional cuprates.     

Interplay of charge, spin, orbital and lattice correlations in colossal magnetoresistance manganites

We derive a realistic microscopic model for doped colossal magnetoresistance manganites, which includes the dynamics of charge, spin, orbital and lattice degrees of freedom on a quantum mechanical level. The model respects the SU(2) spin symmetry and the full multiplet structure of the manganese ions within the cubic lattice. Concentrating on the hole doped domain ( 0≤x≤0.5) we study the influence of the electron-lattice interaction on spin and orbital correlations by means of exact diagonalisation techniques. We find that the lattice can cause a considerable suppression of the coupling between spin and orbital degrees of freedom and show how changes in the magnetic correlations are reflected in dynamic phonon correlations. In addition, our calculation gives detailed insights into orbital correlations and demonstrates the possibility of complex orbital states. Received 4 September 2002 / Received in final form 8 November 2002 Published online 31 December 2002     

Resonant Einstein-de Haas effect in a rubidium condensate

We theoretically consider a spin polarized, optically trapped condensate of 87Rb atoms in F=1. We observe a transfer of atoms to other Zeeman states due to the dipolar interaction which couples the spin and the orbital degrees of freedom. Therefore the transferred atoms acquire an orbital angular momentum. This is a realization of the Einstein-de Haas effect in systems of cold gases. We find resonances which make this phenomenon observable even in very weak dipolar systems, when the Zeeman energy difference on transfer is fully converted to rotational kinetic energy.     

Magnetic-field switching of crystal structure in an orbital-spin-coupled system: MnV2O4

We studied the magnetic and structural properties of spinel MnV2O4, which has S=5/2 spin with no orbital degrees of freedom on the Mn2+ site and S=1 spin and three orbital degrees of freedom on the V3+ site. We found that the ferrimagnetic ordering at TN=56.5K and the structural phase transition at Ts=53.5K are closely correlated in this compound and found a switching of crystal structure between cubic and tetragonal phases by the magnetic field. This phenomenon can be explained by the coupling between orbital and spin degrees of freedom in the t2g states of the V site.     

Dilution effects in two-dimensional quantum orbital systems

Interacting orbital degrees of freedom in a Mott insulator are essentially directional and frustrated. In this Letter, the effect of dilution in a quantum-orbital system with this kind of interaction is studied by analyzing a minimal orbital model which we call the two-dimensional quantum compass model. We find that the decrease of the ordering temperature due to dilution is stronger than that in spin models, but it is also much weaker than that of the classical model. The difference between the classical and the quantum-orbital systems arises from the enhancement of the effective dimensionality due to quantum fluctuations.     

Mg, Sr掺杂CaF2电子结构及光学性质的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理方法对纯CaF2晶体和Mg、Sr掺杂CaF2体系的晶体结构、电学以及光学性质进行了详细的对比研究, 结果表明: 与纯CaF2晶体相比, 掺杂体系的带隙变窄且形成新的态密度峰, 费米面附近出现F与Mg、Sr原子间轨道杂化加强现象. 另外, 掺杂体系仅表现出介电性质, 其对紫外光的吸收强度大大减弱, 而Ca7SrF16掺杂体系在25.44 eV处产生新的小吸收峰. CaF2晶体掺入Mg、Sr原子后, 体系在紫外光区的消光系数减小且对紫外光的透过率增大. 此外, 掺杂体系的反射谱峰和损失函数峰均发生红移且峰值显著降低.     

Mg, Sr掺杂CaF2电子结构及光学性质的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理方法对纯CaF2晶体和Mg、Sr掺杂CaF2体系的晶体结构、电学以及光学性质进行了详细的对比研究, 结果表明: 与纯CaF2晶体相比, 掺杂体系的带隙变窄且形成新的态密度峰, 费米面附近出现F与Mg、Sr原子间轨道杂化加强现象. 另外, 掺杂体系仅表现出介电性质, 其对紫外光的吸收强度大大减弱, 而Ca7SrF16掺杂体系在25.44 eV处产生新的小吸收峰. CaF2晶体掺入Mg、Sr原子后, 体系在紫外光区的消光系数减小且对紫外光的透过率增大. 此外, 掺杂体系的反射谱峰和损失函数峰均发生红移且峰值显著降低.     

Intrinsic coupling of orbital excitations to spin fluctuations in Mott insulators

We show how the general and basic asymmetry between two fundamental degrees of freedom present in strongly correlated oxides, spin and orbital, has very profound repercussions on the elementary spin and orbital excitations. Whereas the magnons remain largely unaffected, orbitons become inherently coupled with spin fluctuations in spin-orbital models with antiferromagnetic and ferro-orbital ordered ground states. The composite orbiton-magnon modes that emerge fractionalize again in one dimension, giving rise to spin-orbital separation in the peculiar regime where spinons are faster than orbitons.     

Role of local geometry in the spin and orbital structure of transition metal compounds

We analyze the role of local geometry in the spin and orbital interaction in transition metal compounds with orbital degeneracy. We stress that the tendency observed in the most studied case (transition metals in O₆ octahedra with one common oxygen—common corner of neighboring octahedra—and with ~180° metal–oxygen–metal bonds), that ferro-orbital ordering renders antiferro-spin coupling and, vice versa, antiferro-orbitals give ferro-spin ordering, is not valid in the general case, in particular, for octahedra with a common edge and with ~90° M–O–M bonds. Special attention is paid to the “third case,” that of neighboring octahedra with a common face (three common oxygens), which has largely been disregarded until now, although there are many real systems with this geometry. Interestingly enough, the spin-orbit exchange in this case turns out to be simpler and more symmetric than in the first two cases. We also consider, which form the effective exchange takes for different geometries in the case of strong spin–orbit coupling.     

Orbital liquid in three-dimensional mott insulator: LaTiO3

We present a theory of spin and orbital states in Mott insulator LaTiO3. The spin-orbital superexchange interaction between d(1)(t(2g)) ions in cubic crystal suffers from a pathological degeneracy of orbital states at the classical level. Quantum effects remove this degeneracy and result in the formation of the coherent ground state, in which the orbital moment of t(2g) level is fully quenched. We find a finite gap for orbital excitations. Such a disordered state of local degrees of freedom on unfrustrated, simple cubic lattice is highly unusual. Orbital liquid state naturally explains observed anomalies of LaTiO3.     

Orbital frustration at the origin of the magnetic behavior in LiNiO2

We report on the ESR, magnetization, and magnetic susceptibility measurements performed over a large temperature range, from 1.5 to 750 K, on high-quality stoichiometric LiNiO2. We find that this compound displays two distinct temperature regions where its magnetic behavior is anomalous. With the help of a statistical model based on the Kugel'-Khomskii Hamiltonian, we show that below T(of) approximately 400 K, an orbitally frustrated state characteristic of the triangular lattice is established. This then gives a solution to the long-standing controversial problem of the magnetic behavior in LiNiO2.     

Tunable topological quantum states in three- and two-dimensional materials

We review our theoretical advances in tunable topological quantum states in three- and twodimensional materials with strong spin–orbital couplings. In three-dimensional systems, we propose a new tunable topological insulator, bismuth-based skutterudites in which topological insulating states can be induced by external strains. The orbitals involved in the topological band-inversion process are the d- and p-orbitals, unlike typical topological insulators such as Bi₂Se₃and BiTeI, where only the p-orbitals are involved in the band-inversion process. Owing to the presence of large d-electronic states, the electronic interaction in our proposed topological insulator is much stronger than that in other conventional topological insulators. In two-dimensional systems, we investigated 3d-transition-metal-doped silicene. Using both an analytical model and first-principles Wannier interpolation, we demonstrate that silicene decorated with certain 3d transition metals such as vanadium can sustain a stable quantum anomalous Hall effect. We also predict that the quantum valley Hall effect and electrically tunable topological states could be realized in certain transition-metal-doped silicenes where the energy band inversion occurs. These findings provide realistic materials in which topological states could be arbitrarily controlled.     

On the Ground State of Spin Systems with Orbital Degeneracy

In order to understand the properties of the spin system with orbital degeneracy,we first study the ground state of the SU(4) spin-orbital model on a square lattice.The mean-field results suggest that for a small Hund‘s interaction,the flavor liquid state is stable against the solid state,but with sufficient deviation from the SU(4) limit the long-range order may be attained in 2D system.Furthermore,we employ a variational approach to calculate the phase diagram of the ground state and the temperature-dependent susceptibility by taking into account the Hund‘s interaction and the anisotropy in orbital wavefunctions.Finally,the implications for the experimental observations on the material,LiNiO2,are discussed.     

Structural properties and charge ordered states in RMnO3 (R=La, Pr, Nd, Ca, Sr) and (La, Sr)2NiO4

Structural distortions arising from the condensations of two essential kinds of phonon modes: the triply degenerate rotational modes (phix, phiy, phiz) of MnO(6) and the doubly degenerate Jahn-Teller active modes (Q1, Q2) have been systematically investigated in the perovskite manganites. Microstructural features associated with certain types of distortions have been observed by transmission electron microscopy (TEM). In RMnO(3) and La(Sr)(2)NiO(4), we characterize the local structure, charge ordered states and orbital ordering by means of low-temperature TEM. We present direct evidence that the stripe modulation in La(Sr)(2)NiO(4) is indeed one-dimensional within each NiO(2) plane. Several typical kinds of defect structures, including antiphase boundaries and the 90 degrees -twin domains, appear commonly in the charge-ordered states.