Size dependence of optical activities in helical polymers.

Chiroptical properties of helical polymers do not always align with the sum of the local contributions of their unit cells. This study investigates the discrepancy in optical rotatory strength between local and global structures using a right-handed helical polyacetylene model. The chirality is examined through density functional theory (DFT) calculations. The analysis reveals that, at higher degrees of polymerization, the contribution of chirality from the helical strand generally surpasses the partial chirality from the local structure. The ratio of local contribution to total contribution is deduced within the framework of crystal orbital theory, and a numerical method using Wannier functions is presented for evaluation.

Unconventional Flat Chern Bands and 2e Charges in Skyrmionic Moiré Superlattices.

The interplay of topological characteristics in real space and reciprocal space can lead to the emergence of unconventional topological phases. In this Letter, we implement a novel mechanism for generating higher-Chern flat bands on the basis of twisted bilayer graphene (TBG) coupled to topological magnetic structures in the form of the skyrmion lattice. In particular, we discover a scenario for generating |C| = 2 dispersionless electronic bands when the skyrmion periodicity and the moiré periodicity match. Following the Wilczek argument, the statistics of the charge-carrying excitations in this case is bosonic, characterized by electronic charge Q = 2e, which is even in units of electron charge e. The skyrmion coupling strength triggering the topological phase transition is realistic, with its lower bound estimated as 4 meV. The Hofstadter butterfly spectrum results in an unexpected quantum Hall conductance sequence ±2e2h,±4e2h,... for TBG with the skyrmion order.

Crystal Field Effect and Electric Field Screening in Multilayer Graphene with and without Twist.

We address the intrinsic polarization and screening of an external electric field in a broad range of ordered and twisted configurations of multilayer graphene, using an ab initio approach combining density functional theory and the Wannier function formalism. We show that multilayer graphene is intrinsically polarized due to the crystal field effect, an effect that is often neglected in tight-binding models of twisted bilayer graphene and similar systems. This intrinsic polarization of the order of up to a few tens of millielectronvolts has different out-of-plane alignments in ordered and twisted graphene multilayers, while the in-plane potential modulation is found to be much stronger in twisted systems. We further investigate the dielectric permittivity ε in same multilayer graphene configurations at different electric field strengths. Our findings establish a deep insight into intrinsic and extrinsic polarization in graphene multilayers and provide parameters necessary for building accurate models of these systems.

Time-dependent density functional theory study on direction-dependent electron and hole transfer processes in molecular systems.

We report on real-time time-dependent density functional theory calculations on direction-dependent electron and hole transfer processes in molecular systems. As a model system, we focus on α-sulfur. It is shown that time scale of the electron transfer process from a negatively charged S8 molecule to a neighboring neutral monomer is comparable to that of a strong infrared-active molecular vibrations of the dimer with one negatively charged monomer. This results in a strong coupling between the electrons and the nuclei motion which eventually leads to S8 ring opening before the electron transfer process is completed. The open-ring structure is found to be stable. The similar infrared-active peak in the case of hole transfer, however, is shown to be very weak and hence no significant scattering by the nuclei is possible. The presented approach to study the charge transfer processes in sulfur has direct applications in the increasingly growing research field of charge transport in molecular systems. © 2017 Wiley Periodicals, Inc.

Quasimolecules in Compressed Lithium.

Under high pressure, some materials form electrides, with valence electrons separated from all atoms and occupying interstitial regions. This is often accompanied by semiconducting or insulating behavior. The interstitial quasiatoms (ISQ) that characterize some high pressure electrides have been postulated to show some of the chemical features of atoms, including the potential of forming covalent bonds. It is argued that in the observed high-pressure semiconducting Li phase (oC40, Aba2), an example of such quasimolecules is realized. The theoretical evaluation of electron density, electron localization function, Wannier orbitals, and bond indices forms the evidence for covalently bonded ISQ pairs in this material. The quasimolecule concept thus provides a simple chemical perspective on the unusual insulating behavior of such materials, complementing the physical picture previously presented where the global crystal symmetry of the system plays the major role.

Efficient "on-the-fly" calculation of Raman spectra from ab-initio molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water.

We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra.

Origins of multi-sublattice magnetism and superexchange interactions in double-double perovskite CaMnCrSbO6.

The multi-sublattice magnetism and electronic structure in double-double perovskite compound CaMnCrSbO6is explored using density functional theory. The bulk magnetization and neutron diffraction suggest a ferrimagnetic order (TC∼49 K) between between Mn2+and Cr3+spins. Due to the non-equivalent Mn atoms (labelled as Mn(1) and Mn(2) which have tetrahedral and planar oxygen coordinations, respectively) and the Cr atom in the centre of distorted oxygen octahedron in the unit cell, the exchange interactions are more complex than that expected from a two sublattice magnetic system. The separations between the on-site energies of thed-orbitals of Mn(1), Mn(2) and Cr obtained from Wannier function analysis are in agreement with their expected crystal field splitting. While the DOS obtained from non spin-polarized calculations show a metallic character, starting from HubbardU = 0 eV the spin-polarized electronic structure calculations yield a ferrimagnetic insulating ground state. The band gap increases withUeff(U - J), thereby showing a Mott-Hubbard nature of the system. The inclusion of anti-site disorder in the calculations show decrease in band-gap and also reduction in the total magnetic moment. Due to the ∼90∘superexchange, nearest neighbour exchange constants obtained from DFT are an order of magnitude smaller than those reported for various magnetic perovskite and double-perovskite compounds. The Mn(1)-O-Mn(2) (out of plane and in-plane), Mn(1)-O-Cr and Mn(2)-O-Cr superexchange interactions are found to be anti-ferromagnetic, while the Cr-O-O-Cr super-superexchange is found to be ferromagnetic. The Mn(2)-O-Cr superexchange is weaker than the Mn(1)-O-Cr super-exchange, thus effectively resulting in ferrimagnetism. From a simple 3-site Hubbard model, we derived expressions for the antiferromagnetic superexchange strengthJAFMand also for the weaker ferromagneticJFM. The relative strengths ofJAFMfor the various superexchange interactions are in agreement with those obtained from DFT. The expression for Cr-O-O-Cr super-superexchange strength (J~SS), which has been derived considering a 4-site Hubbard model, predicts a ferromagnetic exchange in agreement with DFT. Finally, our mean field calculations reveal that assuming a set of four magnetic sub-lattices for Mn2+spins and a single magnetic sublattice for Cr3+spins yields a much improvedTC, while a simple two magnetic sublattice model yields a much higherTC.

Impact of Polarity Mismatch in Infinite-Layer Nickelates.

The recent discovery of superconductivity in infinite-layer Sr-doped NdNiO2 grown on SrTiO3(001) provides a new platform to explore the conducting mechanism of unconventional superconductors. However, the electronic structure of infinite-layer nickelates remains controversial. In this paper, we systematically compare the structural and electronic properties of NdNiO2 films grown on SrTiO3 and LaAlO3 substrates using first-principles calculations. Our results show that the lattice reconstruction accompanied by electronic reconstruction occurs in nickelate films on both substrates. Although both heterostructures (HSs) are conducting at the interface, the SrTiO3-based HS shows distinct atomic displacement in the interfacial TiO2 layer and significant electron accumulation deep into three SrTiO3 layers below the interface, while the LaAlO3-based HS shows negligible atomic displacement and electron localization in the interfacial AlO2 layer, reflecting the impact of polarity mismatch on the electronic structure. Further, Wannier function calculations reveal that the interface stress has no obvious effect on the splitting energy and hopping integral between Ni 3d and Nd-layer orbitals. Although the hybridization between Ni 3dx2-y2 and Nd 5d orbitals is tiny, the hybridization between the Ni 3dx2-y2 orbital and an itinerant interstitial s (IIS) orbital is significantly strong in both cases, suggesting that the IIS orbital may play a critical role in the superconductivity of nickelates.

Electronic Structure and Minimal Models for Flat and Corrugated CuO Monolayers: An Ab Initio Study.

CuO atomic thin monolayer (mlCuO) was synthesized recently. Interest in the mlCuO is based on its close relation to CuO2 layers in typical high temperature cuprate superconductors. Here, we present the calculation of the band structure, the density of states and the Fermi surface of the flat mlCuO as well as the corrugated mlCuO within the density functional theory (DFT) in the generalized gradient approximation (GGA). In the flat mlCuO, the Cu-3dx2-y2 band crosses the Fermi level, while the Cu-3dxz,yz hybridized band is located just below it. The corrugation leads to a significant shift of the Cu-3dxz,yz hybridized band down in energy and a degeneracy lifting for the Cu-3dx2-y2 bands. Corrugated mlCuO is more energetically favorable than the flat one. In addition, we compared the electronic structure of the considered CuO monolayers with bulk CuO systems. We also investigated the influence of a crystal lattice strain (which might occur on some interfaces) on the electronic structure of both mlCuO and determined the critical strains of topological Lifshitz transitions. Finally, we proposed a number of different minimal models for the flat and the corrugated mlCuO using projections onto different Wannier functions basis sets and obtained the corresponding Hamiltonian matrix elements in a real space.

Structural, electronic and magnetic properties of weakly correlated metal Sr2CrTiO6: a first principles study.

Structural, electronic and magnetic behaviour of a less-explored material Sr2CrTiO6has been investigated usingabinitiocalculations with generalized gradient approximation (GGA) and GGA +Umethods, whereUis the Hubbard parameter. For each of the three possible Cr/Ti cationic arrangements in the unit cell, considered in this work, the non-magnetic band structure shows distinct traits with significant flat-band regions leading to larget2gdensity of states around the Fermi energy. The Cr4+ion in Sr2CrTiO6, which is ad2system, shows a reverse splitting of thet2gorbitals. The calculated hopping matrix contains non-zero off-diagonal elements between thedxzanddyzorbitals, while thedxyorbitals remain largely unmixed. A minimal tight binding model successfully reproduces the sixt2gbands around the Fermi energy. The Fermi surface shows a two-dimensional nesting feature for the layered arrangement of Cr and Ti atoms. Fixed spin moment studies suggest that the magnetism in this compound cannot be explained by Stoner's criterion of an itinerant band ferromagnet. In the absence of HubbardUterm, the ground state is a half-metallic ferromagnet. Calculations for the anti-ferromagnetic spin arrangement show re-arrangement of orbital character resulting in (a) narrowdxz/dyzbands and sharp peaks in the density of states at the Fermi energy and (b) highly dispersivedxybands with a broader density of states around the Fermi energy. The metallicity persists even with increasingUfor both the spin arrangements, thus suggesting that Sr2CrTiO6belongs to the class of weakly correlated metals, while the shifting of O 2pstates towards the Fermi energy withUindicates a negative charge-transfer character in Sr2CrTiO6.

Floquet-Dirac fermions in monolayer graphene by Wannier functions.

Wannier functions have been widely applied in the study of topological properties and Floquet-Bloch bands of materials. Usually, the real-space Wannier functions are linked to thek-space Hamiltonian by two types of Fourier transform (FT), namely lattice-gauge FT (LGFT) and atomic-gauge FT (AGFT), but the differences between these two FTs on Floquet-Bloch bands have rarely been addressed. Taking monolayer graphene as an example, we demonstrate that LGFT gives different topological descriptions on the Floquet-Bloch bands for the structurally equivalent directions which are obviously unphysical, while AGFT is immune to this dilemma. We introduce the atomic-laser periodic effect to explain the different Floquet-Bloch bands between the LGFT and AGFT. Using AGFT, we showed that linearly polarized laser could effectively manipulate the properties of the Dirac fermions in graphene, such as the location, generation and annihilation of Dirac points. This proposal offers not only deeper understanding on the role of Wannier functions in solving the Floquet systems, but also a promising platform to study the interaction between the time-periodic laser field and materials.

Quantum computation for predicting electron and phonon properties of solids.

Quantum chemistry is one of the most promising near-term applications of quantum computers. Quantum algorithms such as variational quantum eigen solver (VQE) and variational quantum deflation (VQD) algorithms have been mainly applied for molecular systems and there is a need to implement such methods for periodic solids. Using Wannier tight-binding Hamiltonian (WTBH) approaches, we demonstrate the application of VQE and VQD to accurately predict both electronic and phonon bandstructure properties of several elemental as well as multi-component solid-state materials. We apply VQE-VQD calculations for 307 spin-orbit coupling based electronic WTBHs and 933 finite-difference based phonon WTBHs. Also, we discuss a workflow for using VQD with lattice Green's function that can be used for solving dynamical mean-field theory problems. The WTBH model solvers can be used for testing other quantum algorithms and models also.

Full Assignment of Ab-Initio Raman Spectra at Finite Temperatures Using Wannier Polarizabilities: Application to Cyclohexane Molecule in Gas Phase.

We demonstrate how to fully ascribe Raman peaks simulated using ab initio molecular dynamics to specific vibrations in the structure at finite temperatures by means of Wannier functions. Here, we adopt our newly introduced method for the simulation of the Raman spectra in which the total polarizability of the system is expressed as a sum over Wannier polarizabilities. The assignment is then based on the calculation of partial Raman activities arising from self- and/or cross-correlations between different types of Wannier functions in the system. Different types of Wannier functions can be distinguished based on their spatial spread. To demonstrate the predictive power of this approach, we applied it to the case of a cyclohexane molecule in the gas phase and were able to fully assign the simulated Raman peaks.

Analysis of a capped carbon nanotube by linear-scaling density-functional theory.

The apex region of a capped (5,5) carbon nanotube (CNT) has been modelled with the DFT package ONETEP, using boundary conditions provided by a classical calculation with a conducting surface in place of the CNT. Results from the DFT solution include the Fermi level and the physical distribution and energies of individual orbitals for the CNT tip. Application of an external electric field changes the orbital number of the highest occupied molecular orbital (HOMO) and consequently changes its distribution on the CNT.

Investigation of real materials with strong electronic correlations by the LDA+DMFT method.

Materials with strong electronic correlations are at the cutting edge of experimental and theoretical studies, capturing the attention of researchers for a great variety of interesting phenomena: metal-insulator, phase and magnetic spin transitions, `heavy fermion' systems, interplay between magnetic order and superconductivity, appearance and disappearance of local magnetic moments, and transport property anomalies. It is clear that the richness of physical phenomena for these compounds is a result of partially filled 3d, 4f or 5f electron shells with local magnetic moments preserved in the solid state. Strong interactions of d and f electrons with each other and with itinerant electronic states of the material are responsible for its anomalous properties. Electronic structure calculations for strongly correlated materials should explicitly take into account Coulombic interactions between d or f electrons. Recent advances in this field are related to the development of the LDA+DMFT method, which combines local density approximation (LDA) with dynamical mean-field theory (DMFT) to account for electronic correlation effects. In recent years, LDA+DMFT has allowed the successful treatment not only of simple systems but also of complicated real compounds. Nowadays, the LDA+DMFT method is the state-of-the-art tool for investigating correlated metals and insulators, spin and metal-insulator transitions (MIT) in transition-metal compounds in paramagnetic and magnetically ordered phases.