First-Principles Studies of Structural Evolutions in Cathode Materials LiMO_(2)(M=Co,Mn,Ni)

We explore the structural evolutions of stoichiometric LiMO_(2)using the first-principles calculations combined with the cluster expansion method.We automatically obtain the ground state structures of the stoichiometric LiMO_(2)by just considering the cation orderings in the quasi rock-salt structures and the following structural relaxations due to both the atomic size mismatches and the Jahn–Teller distortions.We point out that,on the one hand,the cation orderings are mainly determined by the nearest,the second nearest,and the third nearest cation interactions and can be obtained from the‘phase diagram’we have built using the relative strengths of effective cluster interaction(ECI).On the other hand,the structural relaxations are dominated by the crystal field splitting(CFS)energies,i.e.,structures with larger CFS energies are more stable.By calculating the ECIs and CFS energies for various structures of LiMO_(2),we clearly show how ECI and CFS play roles in determining the structural evolution mechanism of these systems.

Orbital-Ordering Driven Simultaneous Tunability of Magnetism and Electric Polarization in Strained Monolayer VCl_(3)

Two-dimensional(2D)van der Waals magnetic materials have promising and versatile electronic and magnetic properties in the 2D limit,indicating a considerable potential to advance spintronic applications.Theoretical predictions thus far have not ascertained whether monolayer VCl_(3) is a ferromagnetic(FM)or anti-FM monolayer;this also remains to be experimentally verified.We theoretically investigate the influence of potential factors,including C_(3) symmetry breaking,orbital ordering,epitaxial strain,and charge doping,on the magnetic ground state.Utilizing first-principles calculations,we predict a collinear type-Ⅲ FM ground state in monolayer VCl_(3) with a broken C_(3) symmetry,wherein only the former two of three t_(2g)orbitals(a_(1g),e_(g2)^(π)and e_(g1)^(π))are occupied.The atomic layer thickness and bond angles of monolayer VCl_(3) undergo abrupt changes driven by an orbital ordering switch,resulting in concomitant structural and magnetic phase transitions.Introducing doping to the underlying Cl atoms of monolayer VCl_(3) without C_(3) symmetry simultaneously induces in-and out-of-plane polarizations.This can achieve a multiferroic phase transition if combined with the discovered adjustments of magnetic ground state and polarization magnitude under strain.The establishment of an orbital-ordering driven regulatory mechanism can facilitate deeper exploration and comprehension of magnetic properties of strongly correlated systems in monolayer VCl_(3).

Superexchange Interactions and Magnetic Anisotropy in MnPSe_(3)Monolayer

Two-dimensional van der Waals magnetic materials are of great current interest for their promising applications in spintronics.Using density functional theory calculations in combination with the maximally localized Wannier functions method and the magnetic anisotropy analyses,we study the electronic and magnetic properties of MnPSe_(3)monolayer.Our results show that it is a charge transfer antiferromagnetic(AF)insulator.For this Mn^(2)+3d^(5)system,although it seems straightforward to explain the AF ground state using the direct exchange,we find that the nearly 90oMn-Se-Mn charge transfer type superexchange plays a dominant role in stabilizing the AF ground state.Moreover,our results indicate that,although the shape anisotropy favors an out-of-plane spin orientation,the spin-orbit coupling(SOC)leads to the experimentally observed in-plane spin orientation.We prove that the actual dominant contribution to the magnetic anisotropy comes from the second-order perturbation of the SOC,by analyzing its distribution over the reciprocal space.Using the AF exchange and anisotropy parameters obtained from our calculations,our Monte Carlo simulations give the Néel temperature T_(N)=47 K for MnPSe_(3)monolayer,which agrees with the experimental 40 K.Furthermore,our calculations show that under a uniaxial tensile(compressive)strain,Néel vector would be parallel(perpendicular)to the strain direction,which well reproduces the recent experiments.We also predict that T_(N)would be increased by a compressive strain.

Intrinsic Instability of the Hybrid Halide Perovskite Semiconductor CH3NH3PbI3

The organic-inorganic hybrid perovskite CH3NH3PbI3 has attracted significant interest for its high performance in converting solar light into electrical power with an efficiency exceeding 20%. Unfortunately, chemical stability is one major challenge in the development of CH3NH3PbI3 solar cells. It was commonly assumed that moisture or oxygen in the environment causes the poor stability of hybrid halide perovskites, however, here we show from the first-principles calculations that the room-temperature tetragonal phase of CH3NH3PbI3 is thermodynamically unstable with respect to the phase separation into CH3NH3I ＋ PbI2, i.e., the disproportionation is exothermic, independent of the humidity or oxygen in the atmosphere. When the structure is distorted to the low-temperature orthorhombie phase, the energetic cost of separation increases, but remains small. Contributions from vibrational and configurational entropy at room temperature have been considered, but the instability of CH3NH3PbI3 is unchanged. When I is replaced by Br or CI, Pb by Sn, or the organic cation CH3NH3 by inorganic Cs, the perovskites become more stable and do not phase-separate spontaneously. Our study highlights that the poor chemical stability is intrinsic to CH3NH3PbI3 and suggests that element-substitution may solve the chemical stability problem in hybrid halide perovskite solar cells.

Unexpected low thermal conductivity and large power factor in Dirac semimetal Cd3As2

Thermoelectrics has long been considered as a promising way of power generation for the next decades. So far, extensive efforts have been devoted to the search of ideal thermoelectric materials, which require both high electrical conductivity and low thermal conductivity. Recently, the emerging Dirac semimetal Cd3As2, a three-dimensional analogue of graphene, has been reported to host ultra-high mobility and good electrical conductivity as metals. Here, we report the observation of unexpected low thermal conductivity in Cd3As2, one order of magnitude lower than the conventional metals or semimetals with a similar electrical conductivity, despite the semimetal band structure and high electron mobility. The power factor also reaches a large value of 1.58 mW.m 1 .K-2 at room temperature and remains non-saturated up to 400 K. Corroborating with the first-principles calculations, we find that the thermoelectric performance can be well-modulated by the carrier concentration in a wide range. This work demonstrates the Dirac semimetal Cd3As2 as a potential candidate of thermoelectric materials.

Contrasting Magnetism in Isovalent Layered LaSr3NiRuO4H4 and LaSrNiRuO4 due to Distinct Spin-Orbital States

The recently synthesized first 4d transition-metal oxide-hydride LaSr3NiRuO4H4 with the unusual high H:O ratio surprisingly displays no magnetic order down to 1.8 K. This is in sharp contrast to the similar unusual low-valent Ni^+-Ru^2+ layered oxide LaSrNiRuO4 which has a rather high ferromagnetic(FM) ordering Curie temperature TC^250 K. Using density functional calculations with the aid of crystal field level diagrams and superexchange pictures, we find that the contrasting magnetism is due to the distinct spin-orbital states of the Ru^2+ions(in addition to the common Ni+S = 1/2 state but with a different orbital state): the Ru^2+S = 0 state in LaSr3NiRuO4H4, but the Ru^2+S= 1 state in LaSrNiRuO4. The Ru^2+S = 0 state has the(xy)^2(xz, yz)^4 occupation due to the RuH4O2 octahedral coordination, and then the nonmagnetic Ru2+ions dilute the S= 1/2 Ni^+ sublattice which consequently has a very weak antiferromagnetic superexchange and thus accounts for the presence of no magnetic order down to 1.8 K in LaSr3NiRuO4H4. In strong contrast, the Ru^2+S = 1 state in LaSrNiRuO4 has the(3z^2-r^2)^2(xz, yz)^3(xy)^1 occupation due to the planar square RuO4 coordination, and then the multi-orbital FM superexchange between the S= 1/2 Ni^+ and S= 1 Ru^2+ions gives rise to the high TC in LaSrNiRuO4. This work highlights the importance of spin-orbital states in determining the distinct magnetism.

Directly Determining the Interface Structure and Band Offset of a Large-Lattice-Mismatched CdS/CdTe Heterostructure

The CdS/CdTe heterojunction plays an important role in determining the energy conversion efficiency of CdTe solar cells.However,the interface structure remains unknown,due to the large lattice mismatch between CdS and CdTe,posing great challenges to achieving an understanding of its interfacial effects.By combining a neuralnetwork-based machine-learning method and the stochastic surface walking-based global optimization method,we first train a neural network potential for CdSTe systems with demonstrated robustness and reliability.Based on the above potential,we then use simulated annealing to obtain the optimal structure of the CdS/CdTe interface.We find that the most stable structure has the features of both bulks and disorders.Using the obtained structure,we directly calculate the band offset between CdS and CdTe by aligning the core levels in the heterostructure with those in the bulks,using one-shot first-principles calculations.Our calculated band offset is 0.55 eV,in comparison with 0.70 eV,obtained using other indirect methods.The obtained interface structure should prove useful for further study of the properties of CdTe/CdS heterostructures.Our work also presents an example which is applicable to other complex interfaces.

Magnetic Order and Its Interplay with Structure Phase Transition in van der Waals Ferromagnet VI_(3)

Van der Waals magnet VI_(3) demonstrates intriguing magnetic properties that render it great for use in various applications.However,its microscopic magnetic structure has not been determined yet.Here,we report neutron diffraction and susceptibility measurements in VI_(3) that revealed a ferromagnetic order with the moment direction tilted from the c-axis by ~36° at 4 K.A spin reorientation accompanied by a structure distortion within the honeycomb plane is observed,before the magnetic order completely disappears at TC=50 K.The refined magnetic moment of ~1.3μB at 4 K is much lower than the fully ordered spin moment of 2μB/V^(3+),suggesting the presence of a considerable orbital moment antiparallel to the spin moment and strong spin-orbit coupling in VI_(3).This results in strong magnetoelastic interactions that make the magnetic properties of VI_(3) easily tunable via strain and pressure.

Quantum anomalous Hall effect in real materials

Under a strong magnetic field,the quantum Hall（QH） effect can be observed in two-dimensional electronic gas systems.If the quantized Hall conductivity is acquired in a system without the need of an external magnetic field,then it will give rise to a new quantum state,the quantum anomalous Hall（QAH） state.The QAH state is a novel quantum state that is insulating in the bulk but exhibits unique conducting edge states topologically protected from backscattering and holds great potential for applications in low-power-consumption electronics.The realization of the QAH effect in real materials is of great significance.In this paper,we systematically review the theoretical proposals that have been brought forward to realize the QAH effect in various real material systems or structures,including magnetically doped topological insulators,graphene-based systems,silicene-based systems,two-dimensional organometallic frameworks,quantum wells,and functionalized Sb（111） monolayers,etc.Our paper can help our readers to quickly grasp the recent developments in this field.

Multifunctional two-dimensional van der Waals Janus magnet Cr-based dichalcogenide halides

Two-dimensional van der Waals Janus materials and their heterostructures offer fertile platforms for designing fascinating functionalities.Here,by means of systematic first-principles studies on van der Waals Janus monolayer Cr-based dichalcogenide halides CrYX (Y = S,Se,Te;X = Cl,Br,I),we find that CrSX (X = Cl,Br,I) are the very desirable high T_(C) ferromagnetic semiconductors with an out-of-plane magnetization.Excitingly,by the benefit of the large magnetic moments on ligand S^(2−) anions,the sought-after large-gap quantum anomalous Hall effect and sizable valley splitting can be achieved through the magnetic proximity effect in van der Waals heterostructures CrSBr/Bi_(2)Se_(3)/CrSBr and MoTe_(2)/CrSBr,respectively.Additionally,we show that large Dzyaloshinskii–Moriya interactions give rise to skyrmion states in CrTeX (X = Cl,Br,I) under external magnetic fields.Our work reveals that two-dimensional Janus magnet Cr-based dichalcogenide halides have appealing multifunctionalities in the applications of topological electronic and valleytronic devices.

Strong phonon-magnon coupling of an O/Fe(001) surface

Using density functional calculations,we elucidate the interaction between magnons and phonons on Fe(001)and O/Fe(001)surfaces.The effective Heisenberg exchange parameters between neighbor sites(Ji)were derived by fitting the ab initio spin spiral dispersion relation to a classical Heisenberg model.In bulk Fe,J5bhas a larger amplitude than J2b-J4b.Surface magnons were softer on the Fe(001)surface than in bulk,but were strengthened on the O/Fe(001)surface through strong interactions between the O and Fe atoms.The four calculated high-energy phonon modes of O/Fe(001)excellently agreed with the experimental measurements.The J1in O/Fe(001)decreased significantly with increasing phonon amplitude.Phonon-magnon coupling occurred more easily on O/Fe(001)than on Fe(001).The softening of the magnon on the O/Fe(001)with phonon amplitude was attributed to the reduced amplitude of longitudinal excitations.Magnetic moment of the Fe atom of the second layer(Fe2)was especially sensitive to phonon amplitude,regardless of the motion direction of the Fe2 atoms.

Dynamical Coupling Atomistic and Continuum Simulations

We propose a newmultiscalemethod that couplesmolecular dynamics simulations(MD)at the atomic scale and finite element simulations(FE)at the continuum regime.By constructing the mass matrix and stiffness matrix dependent on coarsening of grids,we find a general form of the equations of motion for the atomic and continuum regions.In order to improve the simulation at finite temperatures,we propose a low-pass phonon filter near the interface between the atomic and continuum regions,which is transparent for low frequency phonons,but dampens the high frequency phonons.