Search

We investigate a strain-induced topological phase transition in the ferromagnetic Janus monolayer MnSbBiS2Te2 using first-principles calculations. The electronic, magnetic, and topological properties are studied under biaxial strain within the range of −8 to +8%. The ground state of monolayer MnSbBiS2Te2 is metallic with an out-of-plane magnetic easy axis. A band gap is opened when a compressive strain between −4% and −7% is applied. We observe a topological phase transition at a biaxial strain of −5%, where the material becomes a Chern insulator exhibiting a quantum anomalous hall (QAH) effect. We find that biaxial strain and spin–orbit coupling (SOC) are responsible for the topological phase transition in MnSbBiS2Te2. In addition, we find that biaxial strain can alter the direction of the magnetic easy axis of MnSbBiS2Te2. The Curie temperature is calculated using the Heisenberg model and is found to be 24 K. This study could pave the way to the design of topological materials with potential applications in spintronics, quantum computing, and dissipationless electronics. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have been intensively developed to be high-performance photovoltaic and optoelectronic materials, where the unique defect tolerance properties are believed to contribute to their excellence. However, defect tolerance, especially for the donors, has not been conclusively understood yet. Using hybrid functional calculations including spin–orbit coupling (SOC), we study the intrinsic defects of γ-CsPbI3. With a sufficiently large supercell and full structural relaxation, we show that most of the donor levels are deep in hybrid functional calculations, but become shallow due to the strong SOC effect, which reconstructs the potential energy surfaces of the donors by eliminating the large structural distortions. By quantifying the variation of electronic and elastic energies associated with defects, we show how the SOC effect changes the energy balance and reconstructs the defect structures. We reveal the decisive role of degeneracy of electronic states in the SOC effect, which significantly downshifts the conduction band minimum due to the quasi-three-fold degeneracy of Pb 6p orbitals, but has little effect on the non-degenerate defect states. [ABSTRACT FROM AUTHOR]

Owing to its novel electronic and magnetic properties, two-dimensional CrI3 has great potential in the application of spintronic devices. However, as an inevitable line defect, the properties of the edges of CrI3 remain elusive. Here, via first-principles calculations with spin–orbit coupling, we investigated the thermodynamic stabilities, electronic and magnetic properties of thirteen CrI3 edges with different structures. We showed that zigzag edges are more stable than armchair edges, and a CrI3 nanoribbon can be either metallic or insulating depending on its chemical growth conditions. The edge stability and associated electronic properties can be understood in terms of the octahedron ligand field and electron counting model. In most cases, both the magnetic moment and Curie temperature can be enhanced by edges, which are in startle contrast to the surfaces of three-dimensional ferromagnetic materials, where a magnetic dead layer is often observed. [ABSTRACT FROM AUTHOR]

Critical topological phases, possessing flat bands, provide a platform to study unique topological properties and transport phenomena under a many-body effect. Here, we propose that critical nodal points and nodal lines or rings can be found in Kagome lattices. After the C3 rotation symmetry of a single-layer Kagome lattice is eliminated, a quadratic nodal point splits into two critical nodal points. When the layered Kagome lattices are stacked into a three-dimensional (3D) structure, critical nodal lines or rings can be generated by tuning the interlayer coupling. Furthermore, we use Kagome graphene as an example to identify that these critical phases could be obtained in real materials. We also discuss flat-band-induced ferromagnetism. It is found that the flat band splits into two spin-polarized bands by hole-doping, and as a result the Dirac-type critical phases evolve into Weyl-type phases. [ABSTRACT FROM AUTHOR]

The photosynthetic protein complex, photosystem II (PSII), conducts the light-driven water-splitting reaction with unrivaled efficiency. Proton-coupled electron transfer (PCET) reactions at the redox-active tyrosine residues are thought to play a critical role in the water-splitting chemistry. Addressing the fundamental question as to why the tyrosine residue, YZ, is kinetically competent in comparison to a symmetrically placed tyrosine residue, YD, is important for the elucidation of the mechanism of PCET in the water-splitting reaction of PSII. Here, using all-quantum-mechanical calculations we study PCET at the YZ and YD residues of PSII. We find that when YZ is in its protein matrix under physiological conditions, the HOMO of YZ constitutes the HOMO of the whole system. In contrast, the HOMO of YD is buried under the electronic states localized elsewhere in the protein matrix and PCET at YD requires the transfer of the phenolic proton, which elevates the HOMO of YD to become the HOMO of the whole system. This leads to the oxidation of YD, albeit on a slower timescale. Our study reveals that the key differences between the electronic structure of YZ and YD are primarily determined by the protonation state of the respective hydrogen-bonding partners, D1-His190 and D2-His189, or more generally by the H-bonding network of the protein matrix. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) B–C–N alloys have recently attracted much attention but unfortunately, Chemical Vapor Deposition (CVD) B–C–N alloys typically phase separate. In spite of that, our analysis of the B–C–N alloy fabricated by electron-beam irradiation suggests that non-phase-separated B–C–N may in fact exist with a carbon concentration up to 14 at%. While this analysis points to a new way to overcome the phase-separation in 2D B–C–N, by first-principles calculations, we show that these B–C–N alloys are made of motifs with even numbers of carbon atoms, in particular, dimers or six-fold rings (in a molecule-like form), embedded in a 2D BN network. Moreover, by tuning the carbon concentration, the band gap of the B–C–N alloys can be reduced by 35% from that of BN. Due to a strong overlap of the wavefunctions at the conduction band and valance band edges, the non-phase-separated B–C–N alloys maintain the strong optical absorption of BN. [ABSTRACT FROM AUTHOR]

Femtosecond lasers (fs) can cause a disparity between electronic and lattice temperatures in the very short period after irradiation. In this relatively cool lattice regime, the material properties can differ drastically from those under thermal equilibrium. In particular, first-principles calculations reveal two general mechanical effects on semiconductors. Firstly, the excitation can induce a negative pressure on the lattice, causing a ＞10% expansion, even for superhard diamond. Secondly, it induces inhomogeneous local forces on the atoms, for both perfect and distorted lattices. In the case of phase-change-memory for Ge2Sb2Te5 and GeTe alloys, such random forces cause a simultaneous phase transition from crystalline to amorphous, which enables faster data writing. These excitation effects are further supported by the time-dependent density functional theory. This work could be an important step in advancing fs laser techniques for the atomic-level control of structures, rather than relying on traditional melting or ablation approaches which often apply to much larger and non-atomic scales. [ABSTRACT FROM AUTHOR]

Water splitting using heterostructures without external bias or sacrificial agents is promising for solving the energy crisis. However, the heterostructures with appropriate band alignments and band gaps have always shown certain degrees of lattice and electron mismatches at their interfaces, which make it difficult for these heterostructures to achieve the theoretically maximum sunlight-driven overall water splitting activity. Here, we made a new type of heterostructure―a crystalline Cu2O/amorphous Ta2O5 heterostructure instead of one with a crystalline/crystalline contact at the interface―which was found to perform overall water splitting with a high apparent quantum yield under visible light irradiation. The results revealed the crystalline/amorphous contact to have a great potential for allowing heterostructures to be used effectively for sunlight-driven overall water splitting. [ABSTRACT FROM AUTHOR]

A semi-Dirac semimetal is a material that exhibits linear band dispersion in one direction and quadratic band dispersion in the orthogonal direction and, therefore, hosts massless and massive fermions at the same point in the momentum space. While a number of interesting physical properties have been predicted in semi-Dirac semimetals, it has been rare to realize such materials in condensed matter. Based on the fact that some honeycomb materials are easily oxidized or chemically absorb other atoms, here, we theoretically propose an approach of modifying their band structures by covalent addition of group-VI elements and strain engineering. We predict a silicene oxide with the chemical formula of Si2O to be a candidate semi-Dirac semimetal. Our approach is backed by the analysis and understanding of the effect of p-orbital frustration on the band structure of graphene-like materials. [ABSTRACT FROM AUTHOR]

Using density functional theory calculation we investigate the carbon doping of anatase TiO2, a technique widely studied for visible-light driven water splitting. By a detailed analysis of the thermodynamics of C defects in TiO2, we show that any significant concentration of C dopants in the TiO2 lattice must be a result of non-equilibrium doping, which emphasizes the importance of kinetics stabilized C defects. Based on the band gaps calculated using hybrid density functionals, we exclude the possibility of C occupying Ti lattice sites or interstitial sites to enhance visible-light absorption of TiO2, as extensively discussed in the literature. Also, the recently proposed defect with a CO species occupying two O sites yields a too small band gap for water splitting. Two defects that can effectively reduce the band gap for the water splitting application are identified to be: (1) the CO–VO complex, i.e., a C substituting for O (CO) paired with an O vacancy (VO) and (2) the (C2)2O complex with a C dimer (C2) occupying two neighboring O vacancies. Compared with the CO–VO complex, (C2)2O exhibits strong binding (greater than 2.5 eV) between the two C atoms, which could significantly enhance its kinetic stability to survive from high temperature annealing. With a reduced band gap of about 1.4 eV, carbon dimers could be ideal for kinetic doping of anatase TiO2 to enhance its visible-light activity in photocatalytic reactions. Molecular doping using C2H2 or C2H4 as C precursors has been proposed to introduce the carbon dimers into TiO2. [ABSTRACT FROM AUTHOR]

We demonstrate experimentally a chemical codoping approach that would simultaneously narrow the band gap and control the band edge positions of TiO2 semiconductors. It is shown that a sequential doping scheme with nitrogen (N) leading the way, followed by phosphorus (P), is crucial for the incorporation of both N and P into the anion sites. Various characterization techniques confirm the formation of the N–P bonds, and as a consequence of chemical codoping, the band gap of TiO2 is reduced from 3.2 eV to 1.8 eV. The realization of chemical codoping could be an important step forward in improving the general performance of electronic and optoelectronic materials and devices. [ABSTRACT FROM AUTHOR]

Ripples naturally occur in graphene sheets. First-principles calculations reveal that, by altering the pyramidalization angles of the carbon atoms, these ripples can be used to direct the chemical reactivity of graphene towards hydrogenation. A fraction of the carbon atoms of a rippled graphene, located around the crests and troughs, show significantly increased reactivity. The remaining carbon atoms have comparable reactivity to those in a flat graphene. To illustrate the increased reactivity, we show that hydrogenation becomes exothermic when the characteristic ratio between the amplitude and wavelength reaches ∼0.55. This finding offers a practical chemical venue for regioselectivity control of graphene functionalization. While the rippling does not directly affect the band gap of the graphene, the rippling-induced hydrogenation does. [ABSTRACT FROM AUTHOR]

Correction for 'Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective' by Jun Chai et al., Phys. Chem. Chem. Phys., 2019, 21, 8721–8728. [ABSTRACT FROM AUTHOR]

We investigate a strain-induced topological phase transition in the ferromagnetic Janus monolayer MnSbBiS 2 Te 2 using first-principles calculations. The electronic, magnetic, and topological properties are studied under biaxial strain within the range of -8 to +8%. The ground state of monolayer MnSbBiS 2 Te 2 is metallic with an out-of-plane magnetic easy axis. A band gap is opened when a compressive strain between -4% and -7% is applied. We observe a topological phase transition at a biaxial strain of -5%, where the material becomes a Chern insulator exhibiting a quantum anomalous hall (QAH) effect. We find that biaxial strain and spin-orbit coupling (SOC) are responsible for the topological phase transition in MnSbBiS 2 Te 2 . In addition, we find that biaxial strain can alter the direction of the magnetic easy axis of MnSbBiS 2 Te 2 . The Curie temperature is calculated using the Heisenberg model and is found to be 24 K. This study could pave the way to the design of topological materials with potential applications in spintronics, quantum computing, and dissipationless electronics.

Owing to its novel electronic and magnetic properties, two-dimensional CrI 3 has great potential in the application of spintronic devices. However, as an inevitable line defect, the properties of the edges of CrI 3 remain elusive. Here, via first-principles calculations with spin-orbit coupling, we investigated the thermodynamic stabilities, electronic and magnetic properties of thirteen CrI 3 edges with different structures. We showed that zigzag edges are more stable than armchair edges, and a CrI 3 nanoribbon can be either metallic or insulating depending on its chemical growth conditions. The edge stability and associated electronic properties can be understood in terms of the octahedron ligand field and electron counting model. In most cases, both the magnetic moment and Curie temperature can be enhanced by edges, which are in startle contrast to the surfaces of three-dimensional ferromagnetic materials, where a magnetic dead layer is often observed.

Using density functional theory calculation we investigate the carbon doping of anatase TiO2, a technique widely studied for visible-light driven water splitting. By a detailed analysis of the thermodynamics of C defects in TiO2, we show that any significant concentration of C dopants in the TiO2 lattice must be a result of non-equilibrium doping, which emphasizes the importance of kinetics stabilized C defects. Based on the band gaps calculated using hybrid density functionals, we exclude the possibility of C occupying Ti lattice sites or interstitial sites to enhance visible-light absorption of TiO2, as extensively discussed in the literature. Also, the recently proposed defect with a CO species occupying two O sites yields a too small band gap for water splitting. Two defects that can effectively reduce the band gap for the water splitting application are identified to be: (1) the CO-VO complex, i.e., a C substituting for O (CO) paired with an O vacancy (VO) and (2) the (C2)2O complex with a C dimer (C2) occupying two neighboring O vacancies. Compared with the CO-VO complex, (C2)2O exhibits strong binding (greater than 2.5 eV) between the two C atoms, which could significantly enhance its kinetic stability to survive from high temperature annealing. With a reduced band gap of about 1.4 eV, carbon dimers could be ideal for kinetic doping of anatase TiO2 to enhance its visible-light activity in photocatalytic reactions. Molecular doping using C2H2 or C2H4 as C precursors has been proposed to introduce the carbon dimers into TiO2.

We demonstrate experimentally a chemical codoping approach that would simultaneously narrow the band gap and control the band edge positions of TiO2 semiconductors. It is shown that a sequential doping scheme with nitrogen (N) leading the way, followed by phosphorus (P), is crucial for the incorporation of both N and P into the anion sites. Various characterization techniques confirm the formation of the N-P bonds, and as a consequence of chemical codoping, the band gap of TiO2 is reduced from 3.2 eV to 1.8 eV. The realization of chemical codoping could be an important step forward in improving the general performance of electronic and optoelectronic materials and devices.

Based on first-principles calculations, we reveal that in the photocatalytic oxygen evolution reaction (OER) at the TiO2/water interface, the formation of an O-O bond always involves the anti-bonding σ2p* state elevated from the valence band into the conduction band of TiO2 regardless of a detailed reaction pathway. The role of photoholes is to deplete this anti-bonding state once it emerges into the band gap. The reaction barrier is thus determined by the onset where photoholes enter the reaction. This process represents a new reaction mechanism, termed nucleus-coupled electron transfer (NCET), where electron transfer is enabled by the movement of nuclei that promotes the reactive orbital to become the frontier orbital. The NCET mechanism for the OER is shown to exhibit an overall kinetic barrier surmountable at room temperature.

Based on first-principles calculations, we designed for the first time a boron-kagome-based two-dimensional MgB6 crystal, in which two boron kagome layers sandwich a triangular magnesium layer. The two-dimensional lattice is metallic with several bands across the Fermi level, and among them a Dirac point appears at the K point of the first Brillouin zone. This metal-stabilized boron kagome system displays electron-phonon coupling, with a superconductivity critical transition temperature of 4.7 K, and thus it is another possible superconducting Mg-B compound besides MgB2. Furthermore, the proposed 2D MgB6 can also be used for hydrogen storage after decoration with Ca. Up to five H2 molecules can be attracted by one Ca with an average binding energy of 0.225 eV. The unique properties of 2D MgB6 will spur broad interest in nanoscience and technology.

We propose titanium-decorated graphene oxide (Ti-GO) as an ideal sorbent for carbon monoxide (CO) capture and separation from gas mixtures. Based on first-principles calculations, Ti-GO exhibits a large binding energy of ~70 kJ mol(-1) for CO molecules, while the binding energies for other gases, such as N(2), CO(2), and CH(4), are significantly smaller. The gas adsorption properties of Ti-GO are independent of the local GO structures once Ti atoms are anchored by the oxygen-containing groups on the GO surface. The strong interaction between CO molecule and Ti is a result of dative bonding, i.e., hybridization between an empty d orbital of Ti and an occupied p orbital of CO. Adsorption isotherms from grand canonical Monte Carlo simulations clearly demonstrate the strong selectivity of Ti-GO for CO adsorption in a mixture with other gas.