Prediction of a two-dimensional high Curie temperature Weyl nodal line kagome semimetal.

Kagome lattices may have numerous exotic physical properties, such as stable ferromagnetism and topological states. Herein, combining the particle swarm structure search method with first-principles calculations, we identify a two-dimensional (2D) kagome Mo2Se3 crystal structure with space group P6/mmm. The results show that 2D kagome Mo2Se3 is a 100% spin-polarized topological nodal line semimetal and exhibits excellent ambient stability. The band crossing points form two nodal loops around the high-symmetry points Γ and K. On the other hand, Mo2Se3 shows intrinsic ferromagnetism with a large magnetic moment of 3.05 µB per Mo atom and magnetic anisotropy energy (MAE) of 4.78 meV. Monte Carlo simulations estimate that Mo2Se3 possesses a high Curie temperature of about 673 K. In addition, its ferromagnetic ground state can be well preserved under external strain, and the MAE can be improved by increasing the strain. More importantly, the position of each nodal line can be adjusted to the Fermi level through hole doping. This multifunctional 2D magnetic material that combines spin and topology has great potential in the field of nanoscale spintronic devices.

Study of electronic and optical properties of CdI2 modulated by electric field: a first-principles study.

We found that an out-of-plane vertical electric field of 1.0 V/Ang helps to maintain the thermodynamic and kinetic stability of monolayer CdI2.The results indicated that the electric field modulates monolayer CdI2 to produce the Mexican-hat electronic state and the giant Stark effect of the vertical electric field on monolayer CdI2 originates from electric field lifting its conduction band. The results based on HSE06 + SOC calculations show that electric field induces strong spin polarization, leading to significant energy level splitting and spin flipping in the valence band. Based on GW0 + BSE, the electric field broadens effective optical response range of monolayer CdI2, the new peak in the optical absorption spectrum under electric field indicates that electric field helps to diminish excitonic effect of monolayer CdI2.

Intrinsic spin, valley and piezoelectric polarizations in room-temperature ferrovalley Janus TiXY (XY = SCl and SeBr) monolayers.

Two-dimensional room-temperature Janus ferrovalley semiconductors with large spin, valley and piezoelectric polarizations provide fertile platforms for designing multifunctional nanodevices. Little research has been reported to date on such materials. Here, using first-principles calculations, we predict two dynamically stable Janus titanium chalcohalide (TiSCl and TiSeBr) monolayers, which are excellent piezoelectric ferrovalley semiconductors with in-plane magnetization and high magnetic transition temperatures (738 and 884 K). When an extrinsic magnetic field is used to force the magnetization along the out-of-plane direction, a large valley polarization (64 and 146 meV) can be generated in the highest valence band with a large spin-orbit coupling by the breaking of time-reversal and space-inversion symmetry, which can be further clarified by a two-band k·p model. This robust valley-contrasting physics characterized by the valley-dependent Berry curvature leads to the anomalous valley Hall effect. It can be observed by suitable hole doping or light irradiation under an in-plane electric field. Besides, we find that the missing mirror symmetry results in giant out-of-plane piezoelectric polarization (2.05 and 2.04 pm V-1). These outstanding properties give the Janus TiSCl and TiSeBr monolayers potential for a wide variety of applications in nanoelectronics, spintronics, valleytronics, piezoelectrics and other demanding areas.

Monolayer gadolinium halides, GdX2 (X = F, Cl, Br): intrinsic ferrovalley materials with spontaneous spin and valley polarizations.

Two-dimensional (2D) intrinsic ferrovalley semiconductors provide unprecedented opportunities to investigate valley physics as well as providing promising device applications due to their exceptional combination of spontaneous spin and valley polarizations. Here, we have predicted from first-principles calculations and Monte Carlo simulations that monolayers (MLs) GdX2 are such extremely rare excellent materials. Apart from their robust stabilities energetically, dynamically, thermally, and mechanically, these 2D materials are found to be semiconducting intrinsic ferromagnets where the magnetic coupling is ascribed to 5d-electron-mediated 4f-4f exchange interactions. Moreover, MLs GdX2 (X = F, Cl, Br) not only exhibit significant magnetic anisotropy energy of 351, 268, and 30 µeV per Gd, but also have a high Curie temperature of 300, 245, and 225 K, respectively. In particular, spontaneous valley polarization in three systems occurs due to the cooperative interplay between the spin-orbit coupling and magnetic exchange interactions, whose magnitude is as sizable as 55, 38, and 82 meV for MLs GdF2, GdCl2, and GdBr2, respectively. Under the action of an in-plane longitudinal electrical field, the valley-contrasting Berry curvatures arising from the broken space-inversion and time-reversal symmetries in MLs GdX2 could yield opposite transverse velocities of the carriers, giving rise to the occurrence of a spin-polarized anomalous valley Hall effect. Overall, these findings render 2D GdX2 a class of promising candidate materials for experimental studies and practical spintronics and valleytronics applications.

Chirality switching of the self-assembled CuPc domains induced by electric field.

Chiral switching of the self-assembled domains of CuPc molecules on the Cd(0001) surface has been investigated by means of a low temperature scanning tunneling microscopy (STM). With the coverage increasing, the CuPc molecules show the structural evolutions from an initial gas-like state to a network phase, a square phase, and finally to a compact phase at full monolayer. In the network and square phases, the achiral CuPc molecules reveal both the point chirality and chiral domains. In particular, the chirality of network domain can be switched from one enantiomer to another driven by the electric filed from a STM tip, which can also lead to the lattice rotation of network phase. These results demonstrate that (i) there is strong interaction between the CuPc molecules and STM tip; (ii) the adsorbed CuPc molecules carry considerable net charge or polarizability due to the charge transfer; (iii) the network phase has a low barrier for the interconversion between right- and left-handed domains. Our findings are significant for the understanding and control of the domain's chirality in the self-assembled structures.

Supramolecular Motors on Graphite Surface Stabilized by Charge States and Hydrogen Bonds.

Molecular motors are nanoscale machines that convert external energies into controlled mechanical movements. In supramolecular motors, the rotator and stator are held together mechanically, and thus the rotation can be essentially barrier free when molecular conformation is negligible. However, nearly all the supramolecular motors appeared in solutions or host-guest complexes. Surface-mounted supramolecular motors have rarely been addressed, even though they are easily manipulated by external fields. Here we report a surface-mounted supramolecular motor assembled by charge states and hydrogen bonds. On a graphite surface, individual ethanol clusters can be charged with a scanning tunneling microscopy tip and then trap the ethanol chains with a permanent dipole moment. Serving as a rotator, the trapped ethanol chains rotate around a charged cluster driven by the inelastic tunneling electrons. Random rotation in clockwise or anticlockwise direction occurs in the chiral molecular chains through chiral flipping. Directional rotation with clockwise chirality can be realized by introducing a chiral branch to the near end of ethanol chains to suppress the chiral flipping with steric hindrance.

Chemisorption-induced two- to three-dimensions structural transformations in gold pentamer (CO)(n)Au5(-) (n =0-5).

Understanding the geometry structures of gold clusters, especially with adsorbates, is essential for designing highly active gold nanocatalysts. Here, CO chemisorption onto the Au5(-) cluster is investigated using the density functional calculations. It is found that chemisorption of CO molecules can induce previously unreported two- to three-dimensions (3D) structural changes. Even a single CO chemisorption induces a major structural change to explain the huge blue-shift in photoelectron spectroscopy (PES). The apex site in the parent Au5(-) cluster is not always the most preferred site for the chemisorption, and two bridged adsorption CO molecules are observed in the lowest-energy (CO)3Au5(-) cluster. A clear splitting is observed in the first PES of (CO)4Au5 (-), and calculated planar and 3D geometries are likely coexisting in the cluster beam. The fifth CO adsorption leads to the structural transformation of Au5 skeleton to create more apex sites to accommodate five CO molecules. The structural properties, together with the vertical electron detachment energy (VDE) and binding energies calculations indicate that the chemisorption-saturated number is 5.

Chiral pinwheel clusters lacking local point chirality.

The supramolecular pinwheel cluster is a unique chiral structure with evident handedness. Previous studies reveal that the chiral pinwheels are composed of chiral or achiral molecules with polar groups, which result in strong intermolecular interactions such as hydrogen-bonding or dipole interactions. Herein, it is shown that the simple linear aromatic molecule, pentacene, can be self-assembled into large chiral pinwheel clusters on the semimetal Bi(111) surface, due to enhanced intermolecular interactions. The pentacene pinwheels reveal two levels of organizational chirality: the chiral hexamers resulting from asymmetric shifting along the long molecular axis, and chiral arrangement of six hexamers with a rotor motif. Furthermore, a new relation between the local point chirality and organizational chirality is identified from the pinwheels: the former is not essential for the latter in 2D pinwheel clusters of the pentacene molecule.