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Magnetic field emerging from the geometric curvature of quantum structure of electrons in a crystal bends electronic trajectory causing anomalous linear and nonlinear electrical Hall effects that have been observed in low symmetry crystals with narrow electronic band gap. We present first-principles theoretical analysis to show that dynamical lowering of crystal symmetry by lattice vibrations results in oscillations in the quantum geometry of electrons which have observable nonlinear Hall signatures. Using these, we introduce a vibrational spectroscopy based on Geometry of Quantum Electronic Structure (GQuES) making specific predictions for the transport and radiative GQuES spectra of 2D materials. As the crystal symmetry is commonly lowered by dynamical fields, GQuES is applicable to a wide range of materials and excitations spanning sub-GHz, THz and infrared frequencies.

Ferroelectric domain walls, recognized as distinct from the bulk in terms of symmetry, structure, and electronic properties, host exotic phenomena including conductive walls, ferroelectric vortices, novel topologies, and negative capacitance. Contrary to conventional understanding, our study reveals that the structure of domain walls in HfO2 closely resembles its bulk. First, our first-principles simulations unveil that the robust ferroelectricity is supported by bosonic pairing of all the anionic phonons in bulk HfO2. Strikingly, the paired phonons strongly bond with each other and successfully reach the center of the domain wall without losing their integrity and produce bulk-like domain walls. We then confirmed preservation of the bulk phonon displacements and consequently full revival of the bulk structure at domain walls via aberration-corrected STEM. The newly found duality between the bulk and the domain wall sheds light on previously enigmatic properties such as zero-energy domain walls, perfect Ising-type polar ordering, and exceptionally robust ferroelectricity at the sub-nm scales. The phonon-pairing discovered here is robust against physical boundaries such as domain walls and enables zero momentum and zero-energy cost local ferroelectric switching. This phenomenon demonstrated in Si-compatible ferroelectrics provides a novel technological platform where data storage on domain walls is as feasible as that within the domains, thereby expanding the potential for high-density data storage and advanced ferroelectric applications., Comment: 24 pages, 4 figures

With first-principles theoretical analysis of the local structure using Bond Orientational Order parameters and Voronoi partitioning, we establish (a) HCP$\rightarrow$BCC structural transformation in high-entropy alloys (HEAs) Nb$_x$(HfZrTi)$_y$ at 16% Nb-concentration, and (b) that the internal lattice distortions (ILDs) peak at the transition. We demonstrate that the relative stability of HCP and BCC structures is driven by energetics, while the overall stability is achieved with contribution from the vibrational entropy that exceeds the configurational entropy of mixing. We show that along with atomic size mismatch, low average number ($< $5) of valence electrons and disparity in the crystal structures of constituent elements are responsible for larger ILDs in Nb$_x$(HfZrTi)$_y$ than in HEAs like Nb$_a$Mo$_b$W$_c$Ta$_d$., Comment: 8 pages, 4 figures

The process of design and discovery of new materials can be significantly expedited and simplified if we can learn effectively from available data. Deep learning (DL) approaches have recently received a lot of interest for their ability to speed up the design of novel materials by predicting material properties with precision close to experiments and ab-initio calculations. The application of deep learning to predict materials properties measured by experiments are valuable yet challenging due to the limited amount of experimental data. Most of the existing approaches to predict properties from computational data have also been directed towards specific material properties. In this work, we extend this approach, by proposing Landscape Crystal Graph Convolution Network(LCGCN), an accurate and transferable deep learning framework based on graph convolutional networks. LCGCN directly learns the potential energy surface (PES) from atomic configurations. This approach can enable transferable models that can predict different material properties. We apply this framework to bulk crystals (i.e. Al2O3), and test it by calculating potential energy surfaces at different temperatures and across different phases of crystal.

Quasi-two-dimensional layered BiSe, a natural super-lattice with Bi2Se3-Bi2-Bi2Se3 units, has recently been predicted to be a dual topological insulator, simultaneously weak topological insulator as well as topological crystalline insulator. Here using structural, transport, spectroscopic measurements and density functional theory calculations, we show that BiSe exhibits rich phase diagram with the emergence of superconductivity with Tc ~8K under pressure. Sequential structural transitions into SnSe-type energetically tangled orthorhombic and CsCl-type cubic structures having distinct superconducting properties are identified at 8 GPa and 13 GPa respectively. Our observation of weak-antilocalization in magneto-conductivity suggests that spin-orbit coupling (SOC) plays a significant role in retaining non-trivial band topology in the trigonal phase with possible realization of 2D topological superconductivity. Theoretical analysis reveals that SOC significantly enhances superconducting Tc of the high-pressure cubic phase through an increase in electron-phonon coupling strength. Simultaneous emergence of Dirac-like surface states suggests cubic BiSe as a suitable candidate for the 3D-topological superconductor., Comment: 15 pages, 5 figures with Supplementary pages

The layered honeycomb lattice iridate Cu$_2$IrO$_3$ is the closest realization of the Kitaev quantum spin liquid, primarily due to the enhanced interlayer separation and nearly ideal honeycomb lattice. We report pressure-induced structural evolution of Cu$_2$IrO$_3$ by powder x-ray diffraction (PXRD) up to $\sim$17 GPa and Raman scattering measurements up to $\sim$25 GPa. A structural phase transition (monoclinic $C2/c \: \rightarrow$ triclinic $P\bar{1}$) is observed with a broad mixed phase pressure range ($\sim$4 to 15 GPa). The triclinic phase consists of heavily distorted honeycomb lattice with Ir-Ir dimer formation and a collapsed interlayer separation. In the stability range of the low-pressure monoclinic phase, structural evolution maintains the Kitaev configuration up to 4 GPa. This is supported by the observed enhanced magnetic frustration in dc susceptibility without emergence of any magnetic ordering and an enhanced dynamic Raman susceptibility. High-pressure resistance measurements up to 25 GPa in the temperature range 1.4--300 K show resilient non-metallic $R$($T$) behaviour with significantly reduced resistivity in the high-pressure phase. The Mott 3D variable-range-hopping conduction with much reduced characteristic energy scale $T_0$ suggests that the high-pressure phase is at the boundary of localized-itinerant crossover. Using first-principles density functional theoretical (DFT) calculations, we find that at ambient pressure $\rm Cu_2IrO_3$ exists in monoclinic $P2_1/c$ phase which is energetically lower than $C2/c$ phase (both the structures are consistent with experimental XRD pattern). DFT reveals structural transition from $P2_1/c$ to $P\bar{1}$ structure at 7 GPa (involving dimerization of Ir-Ir bonds) in agreement with experimentally observed transition pressure., Comment: 32 pages, 11 figures

Topological aspects of electron wavefunction play a crucial role in determining the physical properties of materials. Berry curvature and Chern number are used to define the topological structure of electronic bands. While Berry curvature and its effects in materials have been studied, detecting changes in the topological invariant, Chern number, is challenging. In this regard, twisted double bilayer graphene (TDBG) has emerged as a promising platform to gain electrical control over the Berry curvature hotspots and the valley Chern numbers of its flat bands. In addition, strain induced breaking of the three-fold rotation (C3) symmetry in TDBG, leads to a non-zero first moment of Berry curvature called the Berry curvature dipole (BCD), which can be sensed using nonlinear Hall (NLH) effect. We reveal, using TDBG, that the BCD detects topological transitions in the bands and changes its sign. In TDBG, the perpendicular electric field tunes the valley Chern number and the BCD simultaneously allowing us a tunable system to probe the physics of topological transitions. Furthermore, we find hysteresis of longitudinal and NLH responses with electric field that can be attributed to switching of electric polarization in moir\'e systems. Such a hysteretic response holds promise for next-generation Berry curvature-based memory devices. Probing topological transitions, as we show, can be emulated in other 3D topological systems., Comment: 21 pages, 9 figures, and supplementary information

Bismuth ferrite, BiFeO3, is a multiferroic solid that is attracting increasing attention as a potential photocatalytic material, because the ferroelectric polarisation enhances the separation of photogenerated carriers. With the motivation of finding routes to engineer the band gap and the band alignment, while conserving or enhancing the ferroelectric properties, we have investigated the thermodynamic, electronic and ferroelectric properties of BiCoxFe1 xO3 solid solutions, with 0 < x < 0.13, using density functional theory. We show that the band gap can be reduced from 2.9 eV to 2.1 eV by cobalt substitution, while simultaneously increasing the spontaneous polarisation, which is associated with a notably larger Born effective charge of Co compared to Fe cations. We discuss the interaction between Co impurities, which is strongly attractive and would drive the aggregation of Co, as evidenced by Monte Carlo simulations. Phase separation into a Co-rich phase is therefore predicted to be thermodynamically preferred, and the homogeneous solid solution can only exist in metastable form, protected by slow cation diffusion kinetics. Finally, we discuss the band alignment of pure and Co-substituted BiFeO3 with relevant redox potentials, in the context of its applicability in photocatalysis., Comment: Biblography expanded; typos corrected; improved discussion of photocatalytic applications

We study pressure-induced structural evolution of vanadium diselenide (VSe2), a 1T polymorphic member of the transition metal di-chalcogenide (TMD) family using synchrotron-based powder X-ray diffraction (PXRD) and first-principles density functional theory (DFT). Our XRD results reveal anomalies at P ~4 GPa in c/a ratio, V-Se bond length and Se-V-Se bond angle signalling an isostructural transition. This is followed by a first order structural transition from 1T (space group P-3m1) phase to a 3R (space group R-3m) phase at P ~11 GPa due to sliding of adjacent Se-V-Se layers. We present various scenarios to understand the experimental results within DFT and find that the 1T to 3R transition can be captured only after inclusion of enthalpic correction associated with errors in cell volume with underestimated transition pressure. The abrupt increase in the Debye-Waller factors of Se atoms by a factor of ~4 and hence the anharmonic effects across the structural transition pressure are hitherto not reported so far and hint a possible way to understand the mismatch between the experimental and theoretical transition pressure values., Comment: 18 pages, 5 figures, 1 table

Double-stranded DNA (dsDNA) has been established as an efficient medium for charge migration, bringing it to the forefront of the field of molecular electronics as well as biological research. The charge migration rate is controlled by the electronic couplings between the two nucleobases of DNA/RNA. These electronic couplings strongly depend on the intermolecular geometry and orientation. Estimating these electronic couplings for all the possible relative geometries of molecules using the computationally demanding first-principles calculations requires a lot of time as well as computation resources. In this article, we present a Machine Learning (ML) based model to calculate the electronic coupling between any two bases of dsDNA/dsRNA of any length and sequence and bypass the computationally expensive first-principles calculations. Using the Coulomb matrix representation which encodes the atomic identities and coordinates of the DNA base pairs to prepare the input dataset, we train a feedforward neural network model. Our NN model can predict the electronic couplings between dsDNA base pairs with any structural orientation with a MAE of less than 0.014 eV. We further use the NN predicted electronic coupling values to compute the dsDNA/dsRNA conductance., Comment: Under review at Journal of Chemical Information and Modeling

The insulating ferrimagnet Cu2OSeO3 shows a rich variety of phases such as skyrmion lattice and helical magnetism controlled by interplay of different exchange interactions which can be tuned by external pressure. In this work we have investigated pressure-induced phase transitions at room temperature using synchrotron based x- ray diffraction and Raman scattering measurements. With first-principles theoretical analysis, we show that spin-spin exchange couplings in the ambient cubic phase are affected notably by hydrostatic pressure. The ambient cubic phase transforms to a monoclinic phase above 7 GPa and then to the triclinic phase above 11 GPa. Emergence of new phonon modes in the Raman spectra confirms these structural phase transitions. Notably, upon decompression, the crystal undergoes transition to a new monoclinic structure. Atomic coordinates have been refined in the low pressure cubic phase to capture the Cu-tetrahedra evolution responsible for the earlier reported magnetic behavior under pressure. Our experiments will motivate further studies of its emergent magnetic behavior under pressure., Comment: Submitted to peer-reviewed journal on 18th June,2020. 21 pages, 7 figures, 4 tables

Using first-principles density functional theoretical analysis, we predict coexisting ferroelectric and semi-metallic states in two-dimensional monolayer of h-NbN subjected to electric field and in-plane strain ($\epsilon$). At strains close to $\epsilon$=4.85%, where its out-of-plane spontaneous polarization changes sign without inverting the structure, we demonstrate a hysteretic response of its structure and polarization to electric field, and uncover a three-state (P=$\pm$P$_o$Po, 0) switching during which h-NbN passes through Dirac semi-metallic states. With first-principles evidence for a combination of electronic and phononic ferroelectricity, we present a simple model that captures the energetics of coupled electronic and structural polarization, and show that electronic ferroelectricity arises in a material which is highly polarizable (small bandgap) and exhibits a large electron-phonon coupling leading to anomalous dynamical charges. These insights will guide search for electronic ferroelectrics, and our results on 2D h-NbN will stimulate development of piezo-field effect transistors and devices based on the multi-level logic., Comment: Submitted in PRL, 16 pages, 18 figures

Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It is clear that a small in-plane contraction can explain the Raman peak upshift from bulk to monolayer. However, we show that the larger in-plane parameter in the bulk (compared to the monolayer) results from non-local correlation effects, which cannot be accounted for by local functionals or those with empirical dispersion corrections. Using a non-local-correlation functional, we then investigate the effect of finite temperatures on the Raman signature. We demonstrate that bulk h-BN thermally expands in the direction perpendicular to the layers, while the intralayer distances slightly contract, in agreement with observed experimental behavior. Interestingly, the difference in in-plane cell parameter between bulk and monolayer decreases with temperature, and becomes very small at room temperature. We conclude that the different thermal expansion of bulk and monolayer partially "erases" the intrinsic Raman signature, accounting for its small magnitude in recent experiments on suspended samples., Comment: 6 figures, 2 tables - to appear in Journal of Physics - Condensed Matter

Hexagonal borocarbonitrides (BCN) are a class of 2D materials, which display excellent catalytic activity for water splitting. Here, we report analysis of thermal stability, phonons and thermal conductivity of BCN monolayers over a wide range of temperatures using classical molecular dynamics simulations. Our results show that in contrast to the case of graphene and boron nitride monolayers, the out-of-plane phonons in BCN monolayers induce an asymmetry in the phonon density of states at all temperatures. Despite possessing lower thermal conducting properties compared to graphene and BN monolayers, the BCN nanosheets do not lose thermal conductivity as much as graphene and BN in the studied temperature range of 200-1000 K, and thus, the BCN nanosheets are suitable for thermal interface device applications over a wide range of temperatures. Besides their promising role in water splitting, the above results highlight the possibility of expanding the use of BCN 2D materials in thermal management applications and thermoelectrics., Comment: 6 pages, 4 figures

We uncover the origin of blue luminescence (BL) peak in Mg doped GaN thin film using a combination of experimental X-ray absorption near edge spectroscopy (XANES), first-principles calculations based on density functional theory and full multiple scattering theoretical analysis of various possible defect complexes and their XANES signatures. We demonstrate that a defect complex composed of Mg substituted at Ga site (MgGa) and Mg at interstitial site (Mgi) is primarily responsible for the observed BL by Donor-Acceptor Pair transition (DAP) associated with a deep donor state in the gap. It correlates with a higher (lower) oxidation state of N (Ga) in heavily Mg doped GaN than in its pristine structure, evident in our experiments as well as calculations. Physical and chemical mechanisms identified here point out a route to achieving efficient p-type GaN.

While the atomistic Green's function (AGF) method has the potential to compute spectrally resolved phonon transport across interfaces, most prior formulations of the AGF method provide only the total phonon transmission function that includes contributions from all phonon branches or channels. In this work, we present a formulation of the conventional AGF technique in terms of phonon eigenspectra that provides a natural decomposition of the total transmission function into contributions from various phonon modes. The method involves the use of Dyson and Lippmann-Schwinger equations to determine surface Green's functions from the phonon eigenspectrum of the bulk, and establishes a direct connection between the transmission function and the bulk phonon spectra of the materials forming the interface. We elucidate our formulation of the AGF technique through its application to a microscopic picture of phonon mode conversion at Si-Ge interfaces with atomic intermixing. Intermixing of atoms near the interface is shown to increase the phase space available for phonon mode conversion and to enhance thermal interface conductance at moderate levels of atomic mixing. The eigenspectrum-based AGF (EAGF) method should be useful in determination of microscopic mechanisms of phonon scattering and identification of the specific modes that dominate thermal transport across an interface.

A trigonal phase existing only as small patches on chemically exfoliated few layer, thermodynamically stable 1H phase of MoS2 is believed to influence critically properties of MoS2 based devices. This phase has been most often attributed to the metallic 1T phase. We investigate the electronic structure of chemically exfoliated MoS2 few layered systems using spatially resolved (lesser than 120 nm resolution) photoemission spectroscopy and Raman spectroscopy in conjunction with state-of-the-art electronic structure calculations. On the basis of these results, we establish that the ground state of this phase is a small gap (~90 meV) semiconductor in contrast to most claims in the literature; we also identify the specific trigonal (1T') structure it has among many suggested ones.

The d-band center model of Hammer and N{\o}rskov is widely used in understanding and predicting catalytic activity on transition metal (TM) surfaces. Here, we demonstrate that this model is inadequate for capturing the complete catalytic activity of the magnetically polarized TM surfaces and propose its generalization. We validate the generalized model through comparison of adsorption energies of the NH$_3$ molecule on the surfaces of 3d TMs (V, Cr, Mn, Fe, Co, Ni, Cu and Zn) determined with spin-polarized density functional theory (DFT)-based methods with the predictions of our model. Compared to the conventional d-band model, where the nature of the metal-adsorbate interaction is entirely determined through the energy and the occupation of the d-band center, we emphasize that for the surfaces with high spin polarization, the metal-adsorbate system can be stabilized through a competition of the spin-dependent metal-adsorbate interactions., Comment: 31 pages, including supplemental material

We present a semi-empirical effective Hamiltonian to capture effects of disorder associated with Ba and Sr cations occupying $A$ sites in (Ba$_{x}$Sr$_{1-x}$)TiO$_3$ on its ferroelectric phase transition. Averaging between the parameters of first-principles effective Hamiltonians of end members BaTiO$_3$ and SrTiO$_3$, we include a term with an empirical parameter to capture the local polarization and strains arising from the difference between ionic radii of Ba and Sr. Using mixed-space molecular dynamics of the effective Hamiltonian, we determine $T$-dependent ferroelectric phase transitions in (Ba$_{x}$Sr$_{1-x}$)TiO$_3$ which are in good agreement with experiment. Our scheme of determination of semi-empirical parameters in effective Hamiltonian should be applicable to other perovskite-type ferroelectric solid solutions., Comment: 7 pages, 6 figures, submitted to JPSJ

Motivated by the goal of realizing topological phases in thin films and heterostructures of correlated oxides, we propose here a quantum anomalous Hall insulator (QAHI) in ultrathin films of double perovskites based on mixed 3d-5d or 3d-4d transition metal ions, grown along the [111] direction. Considering the specific case of ultrathin Ba2FeReO6, we present a theoretical analysis of an effective Hamiltonian derived from first-principles. We establish that a strong spin-orbit coupling at Re site, t2g symmetry of the low-energy d-bands, polarity of its [111] orientation of perovskite structure, and mixed 3d-5d chemistry results in room temperature magnetism with a robust QAHI state of Chern number C=1 and a large band-gap. We uncover and highlight a non-relativistic orbital-Rashba-type effect in addition to the spin-orbit coupling, that governs this QAHI state. Our prediction of a large topological band-gap of ~100 meV in electronic structure, and a magnetic transition temperature Tc~300K estimated by Monte Carlo simulations, is expected to stimulate experimental efforts at synthesis of such films and enable possible practical applications of its dissipationless edge currents., Comment: 9 pages, 6 figs, submitted to PRB

The discovery of strong topological insulators led to enormous activity in condensed matter physics and the discovery of new types of topological materials. Bisumth based chalcogenides are exemplary strong three dimensional topological insulators that host an odd number of massless Dirac fermionic states on all surfaces. A departure from this notion is the idea of a weak topological insulator, wherein only certain surface terminations host surface states characterized by an even number of Dirac cones leading to exciting new physics. Experimentally however, weak topological insulators have proven to be elusive. Here, we report a discovery of a weak topological insulator (WTI), BiSe, of the Bi-chalcogenide family with an indirect band gap of 42 meV. Its structural unit consists of bismuth bilayer (Bi$_2$), a known quantum spin hall insulator sandwiched between two units of Bi$_2$Se$_3$ which are three dimensional strong topological insulators. Angle resolved photo-emission spectroscopy (ARPES) measurements on cleaved single crystal flakes along with density fucntional theory (DFT) calculations confirm the existence of weak topological insulating state of BiSe. Additionally, we have carried out magneto-transport measurements on single crystal flakes as well as thin films of BiSe, which exhibit clear signatures of weak anti-localization at low temperatures, consistent with the properties of topological insulators.

From temperature and magnetic field dependent point-contact spectroscopy on the ferromagnetic superconductor Sr$_{0.5}$Ce$_{0.5}$FBiS$_2$ (bulk superconducting $T_c$ = 2.5 K) we observe (a) a pseudogap in the normal state that sustains to a remarkably high temperature of 40 K and (b) two-fold enhancement of $T_c$ upto 5 K in the point-contact geometry. In addition, Andreev reflection spectroscopy reveals a superconducting gap of 6 meV for certain point-contacts suggesting that the mean field $T_c$ of this system could be approximately 40 K, the onset temperature of pseudo-gap. Our results suggest that quantum fluctuations originating from other competing orders in Sr$_{0.5}$Ce$_{0.5}$FBiS$_2$ forbid a global phase coherence at high temperatures thereby suppressing $T_c$. Apart from the known ordering to a ferromagnetic state, our first-principles calculations reveal nesting of a multi-band Fermi surface and a significant electron-phonon coupling that could result in charge density wave-like instabilities., Comment: This is an author-created, un-copyedited version of an article accepted for publication in Journal of Physics: Cond-mat. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (O) and directly interacting with the surface is very relevant to development of PtM (M=3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than O) on (111) surfaces of PtM(Fe,Co,Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy., Comment: Accepted in Chem. Phys. Lett

Kohn-Sham density functional theory (DFT) is a widely-used electronic structure theory for materials as well as molecules. DFT is needed especially for large systems, ab initio molecular dynamics, and high-throughput searches for functional materials. DFT's accuracy and computational efficiency are limited by the approximation to its exchange-correlation energy. Currently, the local density approximation (LDA) and generalized gradient approximations (GGAs) dominate materials computation mainly due to their efficiency. We show here that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-GGA improves significantly over LDA and the standard Perdew-Burke-Ernzerhof GGA for geometries and energies of diversely-bonded materials (including covalent, metallic, ionic, hydrogen, and van der Waals bonds) at comparable efficiency. Thus SCAN may be useful even for soft matter. Often SCAN matches or improves upon the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on materials science.

Using density functional theory calculations, we establish that the half-metallicity of bulk Ba2FeReO6 survives down to 1 nm thickness in BaTiO3/Ba2FeReO6/BaTiO3 heterostructures grown along the (001) and (111) directions. The confinement of the two-dimensional (2D) electron gas in this quantum well structure arises from the suppressed hybridization between Re/Fe d states and unoccupied Ti d states, and it is further strengthened by polar fields for the (111) direction. This mechanism, distinct from the polar catastrophe, leads to an order of magnitude stronger confinement of the 2D electron gas than that at the LaAlO3/SrTiO3 interface. We further show low-energy bands of (111) heterostructure display nontrivial topological character. Our work opens up the possibility of realizing ultrathin spintronic devices.

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C $(x<0.25)$; and (b) the electronic structure of C$_{2x}$B$_{1-x}$N$_{1-x}$ can be further tuned not only with composition $x$, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles., Comment: Physical Chemistry Chemical Physics (2015) - In press

The recent discovery of non-saturating giant positive magnetoresistance in Td-WTe2 has aroused great interest in this material. We have studied the structural, electronic and vibrational properties of bulk and few-layer Td-WTe2 experimentally and theoretically. Spin-orbit coupling is found to govern the semi-metallic character of Td-WTe2. Its structural link with the metallic 1T form provides an understanding of its structural stability. We observe a metal to insulator transition and a change in the sign of the Seebeck coefficient around 373 K. Lattice vibrations in Td-WTe2 have been analyzed by first principle calculations. Out of the 33 possible zone-center Raman active modes, five distinct Raman bands are observed around 112, 118, 134, 165 and 212 cm-1 in bulk Td-WTe2. Based on symmetry analysis and the calculated Raman tensors, we assign the intense bands at 165 cm-1 and 212 cm-1 to the A_1^' and A_1^" modes respectively. We have examined the effect of temperature and the number of layers on the Raman spectrum. Most of the bands of Td-WTe2 stiffen, and the ratio of the integrated intensities of the A_1^" to A_1^' bands decreases in the few-layer sample, while all the bands soften in both bulk and few-layer samples with increasing temperature., Comment: 21 pages, 12 figures, 1 table

The mechanism of heat transfer and the contribution of electron-phonon coupling to thermal conductance of a metal-semiconductor interface remains unclear in the present literature. We report ab initio simulations of a technologically important titanium silicide (metal) - silicon (semiconductor) interface to estimate the Schottky barrier height (SBH), and the strength of electron-phonon and phonon-phonon heat transfer across the interface. The electron and phonon dispersion relations of TiSi$_2$ with C49 structure and the TiSi$_2$-Si interface are obtained using first-principles calculations within the density functional theory (DFT) framework. These are used to estimate electron-phonon linewidths and the associated Eliashberg function that quantifies coupling. We show that the coupling strength of electrons with interfacial phonon modes is of the same order of magnitude as coupling of electrons to phonon modes in the bulk metal, and its contribution to electron-phonon interfacial conductance is comparable to the harmonic phonon-phonon conductance across the interface.

Topological insulators are non-trivial quantum states of matter which exhibit a gap in the electronic structure of their bulk form, but a gapless metallic electronic spectrum at the surface. Here, we predict a uniaxial strain induced electronic topological transition (ETT) from a band to topological insulating state in the rhombohedral phase (space group: R$\bar{3}$m) of As$_2$Te$_3$ ($\beta$-As$_2$Te$_3$) through \textit{first-principles} calculations including spin-orbit coupling within density functional theory. The ETT in $\beta$-As$_2$Te$_3$ is shown to occur at the uniaxial strain $\epsilon_{zz}$ = -0.05 ($\sigma_{zz}$=1.77 GPa), passing through a Weyl metallic state with a single Dirac cone in its electronic structure at the $\Gamma$ point. We demonstrate the ETT through band inversion and reversal of parity of the top of the valence and bottom of the conduction bands leading to change in the $\mathbb{Z}_2$ topological invariant $\nu_0$ from 0 to 1 across the transition. Based on its electronic structure and phonon dispersion, we propose ultra-thin films of As$_2$Te$_3$ to be promising for use in ultra-thin stress sensors, charge pumps and thermoelectrics.

We report observation of 90-degree ferroelectric domain structures in transmission electron microscopy (TEM) of epitaxially-grown films of PbTiO3. Using molecular dynamics (MD) simulations based on first-principles effective Hamiltonian of bulk PbTiO3, we corroborate the occurance of such domains showing that it arises as metastable states only in cooling simulations (as the temperature is lowered) and establish characteristic stability of 90-degree domain structures in PbTiO3. In contrast, such domains do not manifest in similar simulations of BaTiO3. Through a detailed analysis based on energetics and comparison between PbTiO3 and BaTiO3, we find that 90-degree domain structures are energetically favorable only in the former, and the origin of their stability lies in the polarization-strain coupling. Our analysis suggests that they may form in BaTiO3 due to special boundary condition and/or defect-related inhomogeneities., Comment: 7 pages, 5 figures, submitted to PRB

GaFeO3, AlFeO3 and related oxides are ferrimagnetic exhibiting magnetodielectric effect. There has been no evidence to date for ferroelectricity and hence multiferroicity in these oxides. We have investigated these oxides as well as oxides of the composition Al1-x-yGaxFe1+yO3 (x = 0.2, y = 0.2) for possible ferroelectricity by carrying out pyroelectric measurements. These measurements establish the occurrence of ferroelectricity at low temperatures below the N\`eel temperature in these oxides. They also exhibit significant magnetoelectric effect. We have tried to understand the origin of ferroelectricity based on non-centrosymmetric magnetic ordering and disorder by carrying out first-principles calculations., Comment: 21 pages,7 figures

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria - zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached., Comment: 23 pages, 5 figures, 1 table. To appear in Proceedings of the Royal Society A

We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show here that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction of the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration, but reaches a maximum at around 1 mol% Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride, but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase., Comment: 31 pages, 2 tables, 6 figures. Accepted (Sept/2010) for publication in Phys. Rev. B

Using first-principles density functional theory, we study piezoelectricity in short-period superlattices made with combination of ferroelectric and paraelectric components and exhibiting polar discontinuities. We show that piezoelectric response of such a superlattice can be tuned both in terms of sign and magnitude with a choice of its components. As these superlattices with nonswitchable polarization do not undergo ferroelectric transitions, we predict them to exhibit a robust piezoelectric response with weaker temperature dependence compared to their bulk counterparts., Comment: 4 pages, 2 figures

Specific forms of the exchange correlation energy functionals in first-principles density functional theory-based calculations, such as the local density approximation (LDA) and generalized-gradient approximations (GGA), give rise to structural lattice parameters with typical errors of -2% and 2%. Due to a strong coupling between structure and polarization, the order parameter of ferroelectric transitions, they result in large errors in estimation of temperature dependent ferroelectric structural transition properties. Here, we employ a recently developed GGA functional of Wu and Cohen [Phys. Rev. B 73, 235116 (2006)] and determine total-energy surfaces for zone-center distortions of BaTiO3, PbTiO3, and SrTiO3, and compare them with the ones obtained with calculations based on standard LDA and GGA. Confirming that the Wu and Cohen functional allows better estimation of structural properties at 0 K, we determine a new set of parameters defining the effective Hamiltonian for ferroelectric transition in BaTiO3. Using the new set of parameters, we perform molecular-dynamics (MD) simulations under effective pressures p=0.0 GPa, p=-2.0 GPa, and p=-0.005T GPa. The simulations under p=-0.005T GPa, which is for simulating thermal expansion, show a clear improvement in the cubic to tetragonal transition temperature and c/a parameter of its ferroelectric tetragonal phase, while the description of transitions at lower temperatures to orthorhombic and rhombohedral phases is marginally improved. Our findings augur well for use of Wu-Cohen functional in studies of ferroelectrics at nano-scale, particularly in the form of epitaxial films where the properties depend crucially on the lattice mismatch., Comment: 10 pages, 7 figures, 3 tables, resubmitted to PRB

We investigated the rare-earth transition metal oxide series, Ln2CuTiO6 (Ln=Y, Dy, Ho, Er and Yb), crystallizing in the hexagonal structure with non-centrosymmetric P63cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln=Y, exhibit a low temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B-site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected co-operative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant amongst different members of this series are shown to arise from changes in relative contributions from soft polar modes., Comment: Accepted for publication in Phys. Rev. B (21 pages, 2 Table, 8 Figures)