Search

Mixed-anion compounds, which incorporate multiple types of anions into materials, displays tailored crystal structures and physical/chemical properties, garnering immense interests in various applications such as batteries, catalysis, photovoltaics, and thermoelectrics. However, detailed studies regarding correlations between crystal structure, chemical bonding, and thermal/vibrational properties are rare for these compounds, which limits the exploration of mixed-anion compounds for associated thermal applications. In this work, we investigate the lattice dynamics and thermal transport properties of the metal chalcohalides, CuBiSCl2. A high-purity polycrystalline CuBiSCl2 sample, successfully synthesized via modified solid-state synthetic method, exhibits a low lattice thermal conductivity of 0.9-0.6 W m-1 K-1 from 300 to 573 K. By combining various experimental techniques including 3D electron diffraction with theoretical calculations, we elucidate the origin of low lattice thermal conductivity in CuBiSCl2. The stereo-chemical activity of the 6s2 lone pair of Bi3+ favors an asymmetric environment with neighboring anions involving both short and long bond lengths. This particularity often implies weak bonding, low structure dimensionality, and strong anharmonicity, leading to low lattice thermal conductivity. In addition, the strong two-fold linear S-Cu-S coordination with weak Cu -- Cl interactions induces large anisotropic vibration of Cu or structural disorder, which enables strong phonon-phonon scattering and decreases lattice thermal conductivity. The investigations into lattice dynamics and thermal transport properties of CuBiSCl2 broadens the scope of the existing mixed-anion compounds suitable for the associated thermal applications, offering a new avenue for the search of low thermal conductivity materials in low-cost mixed-anion compounds.

We propose a first-principles model of minimum lattice thermal conductivity ($\kappa_{\rm L}^{\rm min}$) based on a unified theoretical treatment of thermal transport in crystals and glasses. We apply this model to thousands of inorganic compounds and discover a universal behavior of $\kappa_{\rm L}^{\rm min}$ in crystals in the high-temperature limit: the isotropically averaged $\kappa_{\rm L}^{\rm min}$ is independent of structural complexity and bounded within a range from $\sim$0.1 to $\sim$2.6 W/[m$\cdot$K], in striking contrast to the conventional phonon gas model which predicts no lower bound. We unveil the underlying physics by showing that for a given parent compound $\kappa_{\rm L}^{\rm min}$ is bounded from below by a value that is approximately insensitive to disorder, but the relative importance of different heat transport channels (phonon gas versus diffuson) depends strongly on the degree of disorder. Moreover, we propose that the diffuson-dominated $\kappa_{\rm L}^{\rm min}$ in complex and disordered compounds might be effectively approximated by the phonon gas model for an ordered compound by averaging out disorder and applying phonon unfolding. With these insights, we further bridge the knowledge gap between our model and the well-known Cahill-Watson-Pohl (CWP) model, rationalizing the successes and limitations of the CWP model in the absence of heat transfer mediated by diffusons. Finally, we construct graph network and random forest machine learning models to extend our predictions to all compounds within the Inorganic Crystal Structure Database (ICSD), which were validated against thermoelectric materials possessing experimentally measured ultralow $\kappa_{\rm L}$. Our work offers a unified understanding of $\kappa_{\rm L}^{\rm min}$, which can guide the rational engineering of materials to achieve $\kappa_{\rm L}^{\rm min}$.

The discovery of high-dielectric materials is crucial to increasing the efficiency of electronic devices and batteries. Here, we report three previously unexplored materials with very high dielectric constants (69 $<$ $\epsilon$ $<$ 101) and large band gaps (2.9$<$ $E_{\text{g}}$(eV) $<$ 5.5) obtained by screening materials databases using statistical optimization algorithms aided by artificial neural networks (ANN). Two of these new dielectrics are mixed-anion compounds (Eu$_5$SiCl$_6$O$_4$ and HoClO), and are shown to be thermodynamically stable against common semiconductors via phase-diagram analysis. We also uncovered four other materials with relatively large dielectric constants (20$<$$\epsilon$$<$40) and band gaps (2.3$<$$E_{\text{g}}$(eV)$<$2.7). While the ANN training data is obtained from Materials Project, the search-space consists of materials from Open Quantum Materials Database (OQMD) - demonstrating a successful implementation of cross-database materials design. Overall, we report dielectric properties of 17 materials calculated using ab-initio calculations, that were selected in our design workflow. The dielectric materials with high dielectric properties predicted in this work open up further experimental research opportunities., Comment: 38 pages, 6 figures, To be published in npj Computational Materials

Intrinsically low lattice thermal conductivity ($\kappa_l$) is a desired requirement in many crystalline solids such as thermal barrier coatings and thermoelectrics. Here, we design an advanced machine-learning (ML) model based on crystal graph convolutional neural network that is insensitive to volumes (i.e., scale) of the input crystal structures to discover novel quaternary chalcogenides, AMM'Q$_3$ (A/M/M'=alkali, alkaline-earth, post-transition metals, lanthanides, Q=chalcogens). Upon screening the thermodynamic stability of $\sim$ 1 million compounds using the ML model iteratively and performing density functional theory (DFT) calculations for a small fraction of compounds, we discover 99 compounds that are validated to be stable in DFT. Taking several DFT-stable compounds, we calculate their $\kappa_l$ using phonon-Boltzmann transport equation, which reveals ultralow-$\kappa_l$ ($<$ 2 Wm$^{-1}$K$^{-1}$ at room-temperature) due to their soft elasticity and strong phonon anharmonicity. Our work demonstrates the high-efficiency of scale-invariant ML model in predicting novel compounds and presents experimental research opportunities with these new compounds.

Semiconductors with very low lattice thermal conductivities are highly desired for applications relevant to thermal energy conversion and management, such as thermoelectrics and thermal barrier coatings. Although the crystal structure and chemical bonding are known to play vital roles in shaping heat transfer behavior, material design approaches of lowering lattice thermal conductivity using chemical bonding principles are uncommon. In this work, we present an effective strategy of weakening interatomic interactions and therefore suppressing lattice thermal conductivity based on chemical bonding principles and develop a high-efficiency approach of discovering low $\kappa_{\rm L}$ materials by screening the local coordination environments of crystalline compounds. The followed first-principles calculations uncover 30 hitherto unexplored compounds with (ultra)low lattice thermal conductivities from thirteen prototype crystal structures contained in the inorganic crystal structure database. Furthermore, we demonstrate an approach of rationally designing high-performance thermoelectrics by additionally incorporating cations with stereochemically active lone-pair electrons. Our results not only provide fundamental insights into the physical origin of the low lattice thermal conductivity in a large family of copper-based compounds but also offer an efficient approach to discovery and design materials with targeted thermal transport properties., Comment: 14 pages, 9 figures

The development of efficient thermal energy management devices such as thermoelectrics, barrier coatings, and thermal data-storage disks often relies on compounds that possess very low lattice thermal conductivity ($\kappa_l$). Here, we present the computational prediction of a large family of 628 thermodynamically stable quaternary chalcogenides, AMM'Q$_3$ (A = alkali/alkaline earth/post-transition metals; M/M' = transition metals, lanthanides; Q = chalcogens) using high-throughput density functional theory (DFT) calculations. We validate the presence of low-$\kappa_l$ in this family of materials by calculating $\kappa_l$ of several predicted stable compounds using the Peierls-Boltzmann transport equation within a first-principles DFT framework. Our analysis reveals that the low-$\kappa_l$ in the AMM'Q$_3$ compounds originates from the presence of either a strong lattice anharmonicity that enhances the phonon scatterings or rattlers cations that lead to multiple scattering channels in their crystal structures. Our predictions suggest new experimental research opportunities in the synthesis and characterization of these stable, low-$\kappa_l$ compounds.

We investigate the microscopic mechanism of ultralow lattice thermal conductivity ($\kappa_l$) of TlInTe$_2$ and its weak temperature dependence using a unified theory of lattice heat transport that considers contributions arising from the particle-like propagation as well as wave-like tunneling of phonons. While we use the Peierls-Boltzmann transport equation (PBTE) to calculate the particle-like contributions ($\kappa_l$(PBTE)), we explicitly calculate the off-diagonal (OD) components of the heat-flux operator within a first-principles density functional theory framework to determine the contributions ($\kappa_l$(OD)) arising from the wave-like tunneling of phonons. At each temperature, T, we anharmonically renormalize the phonon frequencies using the self-consistent phonon theory including quartic anharmonicity, and utilize them to calculate $\kappa_l$(PBTE) and $\kappa_l$(OD). With the combined inclusion of $\kappa_l$(PBTE), $\kappa_l$(OD), and additional grain-boundary scatterings, our calculations successfully reproduce the experimental results. Our analysis shows that large quartic anharmonicity of TlInTe$_2$ (a) strongly hardens the low-energy phonon branches, (b) diminishes the three-phonon scattering processes at finite T, and (c) recovers the weaker than T$^{-1}$ decay of the measured $\kappa_l$.

The class of layered 3D-topological insulators have shown intriguingly anomalous temperature dependence in their thermal expansion coefficients. It was proposed that stacking faults are the origin of the observed anomalous thermal expansion. Here, using femtosecond pump-probe differential reflectivity measurements we probe the carrier and coherently generated totally symmetric A1g1 optical phonons in Bi2Se3. Transient signals also show a low frequency (~GHz) oscillations due to coherent longitudinal acoustic phonons. We extract temperature dependence of optical constants, sound velocity and Young's modulus of Bi2Se3 using the strain pulse propagation model. A remarkable anomalous behavior around ~180 K is observed in the temperature dependence of optical and acoustic phonons as well as the optical constants. First-principles density functional theory (DFT) reveals that thermally activated formation of stacking faults is responsible for the anomalies observed in Bi2Se3, similar to case of Sb2Te3. We also show that inclusion of spin-orbit coupling plays an important role in reducing the total energy difference between the pristine and the faulted structures., Comment: 18 pages, 6 figures

We report high pressure Raman, synchrotron x-ray diffraction and electrical transport studies on Weyl semimetals NbP and TaP along with first-principles density functional theoretical (DFT) analysis. The frequencies of first-order Raman modes of NbP harden with increasing pressure and exhibit a slope change at P$_c$ $\sim$ 9 GPa, and its resistivity exhibits a minimum at P$_c$. The pressure-dependent volume of NbP exhibits a change in its bulk modulus from 207 GPa to 243 GPa at P$_c$. Using DFT calculations, we show that these anomalies are associated with pressure induced Lifshitz transition which involves appearance of electron and hole pockets in its electronic structure. In contrast, results of Raman and synchrotron x-ray diffraction experiments on TaP and DFT calculations show that TaP is quite robust under pressure and does not undergo any phase transition., Comment: 10pages, 12 figures

We report high pressure Raman experiments of Black phosphorus up to 24 GPa. The line widths of first order Raman modes A$^1_g$, B$_{2g}$ and A$^2_g$ of the orthorhombic phase show a minimum at 1.1 GPa. Our first-principles density functional analysis reveals that this is associated with the anomalies in electron-phonon coupling at the semiconductor to topological insulator transition through inversion of valence and conduction bands marking a change from trivial to nontrivial electronic topology. The frequencies of B$_{2g}$ and A$^2_g$ modes become anomalous in the rhombohedral phase at 7.4 GPa, and new modes appearing in the rhombohedral phase show anomalous softening with pressure. This is shown to originate from unusual structural evolution of black phosphorous with pressure, based on first-principles theoretical analysis., Comment: 13pages, 12figures

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.

In recent years, a low pressure transition around P $\sim$ 3 GPa exhibited by the A$_2$B$_3$-type 3D topological insulators is attributed to an electronic topological transition (ETT) for which there is no direct evidence either from theory or experiments. We address this phase transition and other transitions at higher pressure in bismuth selenide (Bi$_2$Se$_3$) using Raman spectroscopy at pressure upto 26.2 GPa. We see clear Raman signatures of an isostructural phase transition at P $\sim$ 2.4 GPa followed by structural transitions at $\sim$ 10 GPa and 16 GPa. First-principles calculations reveal anomalously sharp changes in the structural parameters like the internal angle of the rhombohedral unit cell with a minimum in the c/a ratio near P $\sim$ 3 GPa. While our calculations reveal the associated anomalies in vibrational frequencies and electronic bandgap, the calculated $\mathbb{Z}_2$ invariant and Dirac conical surface electronic structure remain unchanged, showing that there is no change in the electronic topology at the lowest pressure transition., Comment: 18 pages , 6 figures

In this paper we combine the notions of partial metric spaces with negative distances, $G_p$-metric spaces and n-metric spaces together into one structure called the partial n-metric spaces. These are generalizations of all the said structures, and also generalize the notions of $G$-metric and $G_p$-metric spaces to arbitrary finite dimension. We prove Cauchy mapping theorems and other fixed point theorems for such spaces., Comment: arXiv admin note: text overlap with arXiv:1408.5627

A henselian valued field $K$ is called separably tame if its separable-algebraic closure $K^{\operatorname{sep}}$ is a tame extension, that is, the ramification field of the normal extension $K^{\operatorname{sep}}|K$ is separable-algebraically closed. Every separable-algebraically maximal Kaplansky field is a separably tame field, but not conversely. In this paper, we prove Ax-Kochen-Ershov Principles for separably tame fields. This leads to model completeness and completeness results relative to the value group and residue field. As the maximal immediate extensions of separably tame fields are in general not unique, the proofs have to use much deeper valuation theoretical results than those for other classes of valued fields which have already been shown to satisfy Ax-Kochen-Ershov Principles. Our approach also yields alternate proofs of known results for separably closed valued fields., Comment: 30 pages. arXiv admin note: substantial text overlap with arXiv:1304.0194

In this paper we consider partial metric spaces in the sense of O'Neill. We introduce the notions of strong partial metric spaces and Cauchy functions. We prove a fixed point theorem for such spaces and functions that improves Matthews' contraction mapping theorem in two ways. First, the existence of fixed points now holds for a wider class of functions and spaces. Second, our theorem also allows for fixed points with nonzero self-distances. We also prove fixed point theorems for orbitally $r$-contractive and orbitally $\phi_r$-contractive maps. We then apply our results to give alternative proofs of some of the other known fixed point theorems in the context of partial metric spaces., Comment: 19 pages

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.

Kikyo and Shelah showed that if $T$ is a theory with the Strict Order Property in some first-order language $\mathcal{L}$, then in the expanded language $\mathcal{L}_\sigma := \mathcal{L}\cup\{\sigma\}$ with a new unary function symbol $\sigma$, the bigger theory $T_\sigma := T\cup\{``\sigma \mbox{is an} \mathcal{L}\mbox{-automorphism''}\}$ does not have a model companion. We show in this paper that if, however, we restrict the automorphism and consider the theory $T_\sigma$ as the base theory $T$ together with a ``restricted'' class of automorphisms, then $T_\sigma$ can have a model companion in $\mathcal{L}_\sigma$. We show this in the context of linear orders and ordered abelian groups.

The nontrivial electronic topology of a topological insulator is thus far known to display signatures in a robust metallic state at the surface. Here, we establish vibrational anomalies in Raman spectra of the bulk that signify changes in electronic topology: an E2 g phonon softens unusually and its linewidth exhibits an asymmetric peak at the pressure induced electronic topological transition (ETT) in Sb2Se3 crystal. Our first-principles calculations confirm the electronic transition from band to topological insulating state with reversal of parity of electronic bands passing through a metallic state at the ETT, but do not capture the phonon anomalies which involve breakdown of adiabatic approximation due to strongly coupled dynamics of phonons and electrons. Treating this within a four-band model of topological insulators, we elucidate how nonadiabatic renormalization of phonons constitutes readily measurable bulk signatures of an ETT, which will facilitate efforts to develop topological insulators by modifying a band insulator.

In this paper, we give appropriate languages in which the theory of tame fields (of any characteristic) admits (relative) quantifier elimination., Comment: This paper has been withdrawn by the authors due to a crucial error in a proof

The theory of valued difference fields $(K, \sigma, v)$ depends on how the valuation $v$ interacts with the automorphism $\sigma$. Two special cases have already been worked out - the isometric case, where $v(\sigma(x)) = v(x)$ for all $x\in K$, has been worked out by Luc Belair, Angus Macintyre and Thomas Scanlon; and the contractive case, where $v(\sigma(x)) > n\cdot v(x)$ for all $n\in\mathbb{N}$ and $x\in K^\times$ with $v(x) > 0$, has been worked out by Salih Azgin. In this paper we deal with a more general version, called the multiplicative case, where $v(\sigma(x)) = \rho\cdot v(x)$, where $\rho (> 0)$ is interpreted as an element of a real-closed field. We give an axiomatization and prove a relative quantifier elimination theorem for such a theory., Comment: 37 pages