Table of contents

It has been highly desired to provide an accurate and reliable method to calculate core electron binding energies (CEBEs) of crystals and to understand the final state screening effect on a core hole in high resolution x-ray photoelectron spectroscopy (XPS), because the ΔSCF method cannot be simply used for bulk systems. We propose to use the quasiparticle calculation based on many-body perturbation theory for this problem. In this study, CEBEs of band-gapped crystals, silicon, diamond, β-SiC, BN, and AlP, are investigated by means of the GW approximation (GWA) using the full ω integration and compared with the preexisting XPS data. The screening effect on a deep core hole is also investigated in detail by evaluating the relaxation energy (RE) from the core and valence contributions separately. Calculated results show that not only the valence electrons but also the core electrons have an important contribution to the RE, and the GWA have a tendency to underestimate CEBEs due to the excess RE. This underestimation can be improved by introducing the self-screening correction to the GWA. The resulting C1s, B1s, N1s, Si2p, and Al2p CEBEs are in excellent agreement with the experiments within 1 eV absolute error range. The present self-screening corrected GW approach has the capability to achieve the highly accurate prediction of CEBEs without any empirical parameter for band-gapped crystals, and provide a more reliable theoretical approach than the conventional ΔSCF-DFT method.

Kohn–Sham density functional theory (DFT) is routinely used for the fast electronic structure computation of large systems and will most likely continue to be the method of choice for the generation of reliable geometries in the foreseeable future. Here, we present a hierarchy of simplified DFT methods designed for consistent structures and non-covalent interactions of large systems with particular focus on molecular crystals. The covered methods are a minimal basis set Hartree–Fock (HF-3c), a small basis set screened exchange hybrid functional (HSE-3c), and a generalized gradient approximated functional evaluated in a medium-sized basis set (B97-3c), all augmented with semi-classical correction potentials. We give an overview on the methods design, a comprehensive evaluation on established benchmark sets for geometries and lattice energies of molecular crystals, and highlight some realistic applications on large organic crystals with several hundreds of atoms in the primitive unit cell.

In this work, a novel compound Ba₉V₃Se₁₅ with one-dimensional (1D) spin chains was synthesized under high-pressure and high-temperature conditions. It was systematically characterized via structural, magnetic, thermodynamic and transport measurements. Ba₉V₃Se₁₅ crystallizes into a hexagonal structure with a space group of P-6c2 (188) and the lattice constants of a  =  b  =  9.5745(7) Å and c  =  18.7814(4) Å. The crystal structure consists of face-sharing octahedral VSe₆ chains along c axis, which are trimeric and arranged in a triangular lattice in ab-plane. Ba₉V₃Se₁₅ is a semiconductor and undergoes complex magnetic transitions. In the zero-field-cooled (ZFC) process with magnetic field of 10 Oe, Ba₉V₃Se₁₅ sequentially undergoes ferrimagnetic and spin cluster glass transition at 2.5 K and 3.3 K, respectively. When the magnetic field exceeds 50 Oe, only the ferrimagnetic transition can be observed. Above the transition temperature, the specific heat contains a significant magnetic contribution that is proportional to T^1/2. The calculation suggests that the nearest neighbor (NN) intra-chain antiferromagnetic exchange J₁ is much larger than the next nearest neighbor (NNN) intra-chain ferromagnetic exchange J₂. Therefore, Ba₉V₃Se₁₅ can be regarded as an effective ferromagnetic chains with effective spin-1/2 by the formation of the V(2)^(↓)V(1)^(↑)V(2)^(↓) cluster.

In this paper we study the shape characteristics of star-like polymers in various solvent quality using a mesoscopic level of modeling. The dissipative particle dynamics simulations are performed for the homogeneous and four different heterogeneous star polymers with the same molecular weight. We analyse the gyration radius and asphericity at the poor, good and θ-solvent regimes. Detailed explanation based on interplay between enthalpic and entropic contributions to the free energy and analyses on of the asphericity of individual branches are provided to explain the increase of the apsphericity in θ-solvent regime.

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m⁻¹. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

Semiconductor nanowires are interesting candidates for realization of spintronics devices. In this paper we study electronic states and effects of lateral spin–orbit coupling (LSOC) in a one-dimensional asymmetrically biased nanowire using the Hartree–Fock method with Dirac interaction. We have shown that spin polarization can be triggered by LSOC at finite source-drain bias,as a result of numerical noise representing a random magnetic field due to wiring or a random background magnetic field by Earth magnetic field, for instance. The electrons spontaneously arrange into spin rows in the wire due to electron interactions leading to a finite spin polarization. The direction of polarization is, however, random at zero source-drain bias. We have found that LSOC has an effect on orientation of spin rows only in the case when source-drain bias is applied.

We solve the Weyl electron scattered by a spherical step potential barrier. Tuning the incident energy and the potential radius, one can enter both quasiclassical and quantum regimes. Transport features related to far-field currents and integrated cross sections are studied to reveal the preferred forward scattering. In the quasiclassical regime, a strong focusing effect along the incident spherical axis is found in addition to optical caustic patterns. In the quantum regime, at energies of successive angular momentum resonances, a polar aggregation of electron density is found inside the potential. The findings will be useful in transport studies and electronic lens applications in Weyl systems.

Structural stability of Fe₂P is investigated in detail using first-principles calculations based on density functional theory. While the orthorhombic C23 phase is found to be energetically more stable, the experiments suggest it to be hexagonal C22 phase. In the present study, we show that in order to obtain the correct ground state structure of Fe₂P from the first-principles based methods it is utmost necessary to consider the zero-point effects such as zero-point vibrations and spin fluctuations. This study demonstrates an exceptional case where a bulk material is stabilized by quantum effects, which are usually important in low-dimensional materials. Our results also indicate the possibility of magnetic field induced structural quantum phase transition in Fe₂P, which should form the basis for further theoretical and experimental efforts.

The intrinsic parameters of carbon nanotubes (CNTs) such as ionization potential (IP) and electron affinity (EA) are closely related to their unique properties and associated applications. In this work, we demonstrated the success of optimal tuning method based on range-separated (RS) density functionals for both accurate and efficient prediction of vertical IPs and electron affinities (EAs) of a series of armchair single-walled carbon nanotubes C_20nH₂₀ (n  =  2–6) compared to the high-level IP/EA equation-of-motion coupled-cluster method with single and double substitutions (IP/EA-EOM-CCSD). Notably, the resulting frontier orbital energies (–ε_HOMO and –ε_LUMO) from the tuning method exhibit an excellent approximation to the corresponding IPs and EAs, that significantly outperform other conventional density functionals. In addition, it is suggested that the RS density functionals that possess both a fixed amount of exact exchange in the short-range and a correct long-range asymptotic behavior are suitable for calculating electronic structures of finite-sized CNTs. Next the performance of density functionals for description of various molecular properties such as chemical potential, hardness and electrophilicity are assessed as a function of tube length. Thanks to the efficiency and accuracy of this tuning method, the related behaviors of much longer armchair single-walled CNTs until C₂₀₀H₂₀ were studied. Lastly, the present work is proved to provide an efficient theoretical tool for future materials design and reliable characterization of other interesting properties of CNT-based systems.

An accurate theoretical prediction of ionization potential (IP) and electron affinity (EA) is key in understanding complex photochemical processes in aqueous environments. There have been numerous efforts in literature to accurately predict IP and EA of liquid water, however with often conflicting results depending on the level of theory and the underlying water structures. In a recent study based on hybrid-non-self-consistent many-body perturbation theory (MBPT) Gaiduk et al (2018 Nat. Commun. 9 247) predicted an IP of 10.2 eV and EA of 0.2 eV, resulting in an electronic band gap (i.e. electronic gap (IP-EA) as measured by photoelectron spectroscopy) of about 10 eV, redefining the widely cited experimental gap of 8.7 eV in literature. In the present work, we show that GW self-consistency and an implicit vertex correction in MBPT considerably affect recently reported EA values by Gaiduk et al (2018 Nat. Commun. 9 247) by about 1 eV. Furthermore, the choice of pseudo-potential is critical for an accurate determination of the absolute band positions. Consequently, the self-consistent GW approach with an implicit vertex correction based on projector augmented wave (PAW) method on top of quantum water structures predicts an IP of 10.2, an EA of 1.1, a fundamental gap of 9.1 eV and an exciton binding (Eb) energy of 0.9 eV for the first absorption band of liquid water via the Bethe–Salpeter equation (BSE). Only within such a self-consistent approach a simultanously accurate prediction of IP, EA, Eg, Eb is possible.

In this work, we report the effect of random magnetic anisotropy (RMA) on the valence, magnetocaloric and resistivity properties in a glassy intermetallic material Sm₂Ni_0.87Si_2.87. On the basis of detailed studies on the valence band and core level electronic structure, we have established that both the Sm³⁺ and Sm²⁺ ions are present in the system, suggesting the compound to be of mixed valence in nature. The significant observation of positive magnetic entropy change in zero-field cooled measurement has been argued due to the presence of RMA that develops due to local electronic environmental variations between the rare-earth ions in the system. The quantum interference effect caused by the elastic electron–electron interaction is responsible for the resistivity upturn at low-temperature for this disordered metallic conductor.

Recently a new one-dimensional (1D) quantum spin chain system has been reported: catena-dichloro(2-Cl-3Mpy)copper(II), (where 2-Cl-3Mpy=2-chloro-3-methylpyridine). Preliminary calculations and bulk magnetic property measurements indicate that this system does not undergo magnetic ordering down to 1.8 K and is a prime candidate for investigating frustration in a J₁/J₂ system (where the nearest neighbour interactions, J₁, are ferromagnetic and the next nearest neighbour interactions, J₂, are antiferromagnetic). Calculations predicted three possible magnetic interaction strengths for J₁ below 6 meV depending on the orientation of the ligand. For one of the predicted J₁ values, the existence of a quantum critical point is implied.

A deuterated sample of catena-dichloro(2-Cl-3Mpy)copper(II) was synthesised and the excitations measured using inelastic neutron scattering. Scattering indicated the most likely scenario involves spin-chains where each chain consists of only one of the three possible magnetic excitations in this material, rather than the completely random array of exchange interactions within each chain as predicted by Herringer et al (2014 Chem. Eur. J. 20 8355–62). This indicates the possibility of tuning the chemical structure to favour a system which may exhibit a quantum critical point.

Lead zirconate titanate samples are used for their piezoelectric and ferroelectric properties in various types of micro-devices. Epitaxial layers of tetragonal perovskites have a tendency to relax by forming ferroelastic domains. The accommodation of the a/c/a/c polydomain structure on a flat substrate leads to nanoscale deformation gradients which locally influence the polarization by flexoelectric effect. Here, we investigated the deformation fields in epitaxial layers of Pb(Zr_0.2Ti_0.8)O₃ grown on SrTiO₃ substrates using transmission electron microscopy (TEM). We found that the deformation gradients depend on the domain walls inclination ( or to the substrate interface) of the successive domains and we describe three different a/c/a domain configurations: one configuration with parallel a-domains and two configurations with perpendicular a-domains (V-shaped and hat--shaped). In the parallel configuration, the c-domains contain horizontal and vertical gradients of out-of-plane deformation. In the V-shaped and hat--shaped configurations, the c-domains exhibit a bending deformation field with vertical gradients of in-plane deformation. Each of these configurations is expected to have a different influence on the polarization and so the local properties of the film. The deformation gradients were measured using dark-field electron holography, a TEM technique, which offers a good sensitivity (0.1%) and a large field-of-view (hundreds of nanometers). The measurements are compared with finite element simulations.

PbTiO₃ (PT) and PbZrO₃ (PZ) are the two primary blocks of the solid solution PbZr_1−xTi_xO₃ (PZT). They can be modelled in different ways; but, in order to do comparable DFT calculations on PZT, with different values of x, one must find a unique method that can be used for both PT and PZ. In particular, we want to evaluate their vibrational properties to compare them with experimental data. Density functional theory (DFT) is used to perform structure geometry optimizations and electronic structure calculations, both on low- and high-temperature phase. Then, harmonic vibrational frequencies of their low-temperature phase are determined for transverse and longitudinal optical (TO & LO) phonons. Moreover, a detailed study of the eigenvectors shows that accurate calculations are necessary to correctly interpret and understand the IR spectra. In the end, the comparison of our theoretical results with previous experimental and theoretical data confirm the strong potential of the SOGGA (second-order generalized gradient approximation) functional to correctly describe PT, PZ and, hopefully, PZT; especially their structural and vibrational properties.

First-principles calculations are conducted to study the electronic and magnetic states of Mn-doped monolayer MoS₂ under lattice strain. Mn-doped MoS₂ exhibits half-metallic and ferromagnetic (FM) characteristics in which the majority spin channel exhibits metallic features but there is a bandgap in the minority spin channel. The FM state and the total magnetic moment of 1 µ_B are always maintained for the larger supercells of monolayer MoS₂ with only one doped Mn, no matter under tensile or compressive strain. Furthermore, the FM state will be enhanced by the tensile strain if two Mo atoms are substituted by Mn atoms in the monolayer MoS₂. The magnetic moment increases up to 0.50 µ_B per unit cell at a tensile strain of 7%. However, the Mn-doped MoS₂ changes to metallic and antiferromagnetic under compressive strain. The spin polarization of Mn 3d orbitals disappears gradually with increasing compressive strain, and the superexchange interaction between Mn atoms increases gradually. The results suggest that the electronic and magnetic properties of Mn-doped monolayer MoS₂ can be effectively modulated by strain engineering providing insight into application to electronic and spintronic devices.

The critical magnetic properties of a non-centrosymmetric B20 cubic helimagnet Fe_0.6Co_0.4Si are investigated using magnetization isotherms. It belongs to the 3D-Heisenberg universality class with short range magnetic coupling as inferred from the self-consistent critical exponents , , and in combination with exchange interaction . Itinerant magnetic nature of the compound is realized by the Rhodes–Wholfarth analysis. Field-induced weak first (parahelical) to second (parafield-polarized) order transition is reported to occur at low critical field due to the weak spin–orbit coupling arising from the weak Dzyaloshinksii–Moriya interactions. Our study suggests the distinct phenomenological magnetic structures for Fe-based cubic magnets (Fe_1−xCo_xSi and FeGe) and MnSi which cause contrasting physical properties.

The binary intermetallic compound Er₅Pd₂ has been investigated using dc and ac magnetic susceptibilities, magnetic memory effect, isothermal magnetization, non-linear dc susceptibility, heat capacity and magnetocaloric effect studies. Interestingly, even though the compound does not show geometrical frustration it undergoes glassy magnetic phase transition below 17.2 K. Investigation of dc magnetization and heat capacity data divulged absence of long-ranged magnetic ordering. Through the magnetic memory effect, time dependent magnetization and ac susceptibility studies it was revealed that the compound undergoes glass-like freezing below 17.2 K. Analysis of frequency dependence of this transition temperature through scaling and Arrhenius law; along with the Mydosh parameter indicate, that the dynamics in Er₅Pd₂ are due to the presence of strongly interacting superspins rather than individual spins. This phase transition was further investigated by non-linear dc susceptibility and was characterized by static critical exponents γ and δ. Our results indicate that this compound shows the signature of superspin glass at low temperature. Additionally, both conventional and inverse magnetocaloric effect was observed with a large value of magnetic entropy change and relative cooling power. Our results suggest that Er₅Pd₂ can be classified as a superspin glass system with large magnetocaloric effect.