A unified understanding of minimum lattice thermal conductivity.

We propose a first-principles model of minimum lattice thermal conductivity ([Formula: see text]) based on a unified theoretical treatment of thermal transport in crystals and glasses. We apply this model to thousands of inorganic compounds and find a universal behavior of [Formula: see text] in crystals in the high-temperature limit: The isotropically averaged [Formula: see text] is independent of structural complexity and bounded within a range from ∼0.1 to ∼2.6 W/(m 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, [Formula: see text] 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 [Formula: see text] 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 κL. Our work offers a unified understanding of [Formula: see text], which can guide the rational engineering of materials to achieve [Formula: see text].

Microscopic Mechanisms of Glasslike Lattice Thermal Transport in Cubic Cu_{12}Sb_{4}S_{13} Tetrahedrites.

Materials based on cubic tetrahedrites (Cu_{12}Sb_{4}S_{13}) are useful thermoelectrics with unusual thermal and electrical transport properties, such as very low and nearly temperature-independent lattice thermal conductivity (κ_{L}). We explain the microscopic origin of the glasslike κ_{L} in Cu_{12}Sb_{4}S_{13} by explicitly treating anharmonicity up to quartic terms for both phonon energies and phonon scattering rates. We show that the strongly unstable phonon modes associated with trigonally coordinated Cu atoms are anharmonically stabilized above approximately 100 K and continue hardening with increasing temperature in accord with experimental data. This temperature-induced hardening effect reduces scattering of heat carrying acoustic modes by reducing the available phase space for three-phonon processes, thereby balancing the conventional ∝T increase in scattering due to phonon population and yielding nearly temperature-independent κ_{L}. Furthermore, we find that very strong phonon broadening leads to a qualitative breakdown of the conventional phonon-gas model and modify the dominant heat transport mechanism from the particlelike phonon wave packet propagation to incoherent contributions described by the off-diagonal terms in the heat-flux operator, which are typically prevailing in glasses and disordered crystals. Our work paves the way to a deeper understanding of glasslike thermal conductivity in complex crystals with strong anharmonicity.

Particlelike Phonon Propagation Dominates Ultralow Lattice Thermal Conductivity in Crystalline Tl_{3}VSe_{4}.

We investigate the microscopic mechanisms of ultralow lattice thermal conductivity (κ_{l}) in Tl_{3}VSe_{4} by combining a first principles density functional theory based framework of anharmonic lattice dynamics with the Peierls-Boltzmann transport equation for phonons. We include contributions of the three- and four-phonon scattering processes to the phonon lifetimes as well as the temperature dependent anharmonic renormalization of phonon energies arising from an unusually strong quartic anharmonicity in Tl_{3}VSe_{4}. In contrast to a recent report by Mukhopadhyay et al. [Science 360, 1455 (2018)SCIEAS0036-807510.1126/science.aar8072] which suggested that a significant contribution to κ_{l} arises from random walks among uncorrelated oscillators, we show that particlelike propagation of phonon excitations can successfully explain the experimentally observed ultralow κ_{l}. Our findings are further supported by explicit calculations of the off-diagonal terms of the heat current operator, which are found to be small and indicate that wavelike tunneling of heat carrying vibrations is of minor importance. Our results (i) resolve the discrepancy between the theoretical and experimental κ_{l}, (ii) offer new insights into the minimum κ_{l} achievable in Tl_{3}VSe_{4}, and (iii) highlight the importance of high order anharmonicity in low-κ_{l} systems. The methodology demonstrated here may be used to resolve the discrepancies between the experimentally measured and the theoretically calculated κ_{l} in skutterides and perovskites, as well as to understand the glasslike κ_{l} in complex crystals with strong anharmonicity, leading towards the goal of rational design of new materials.

Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3-x.

The short charging times and high power capabilities associated with capacitive energy storage make this approach an attractive alternative to batteries. One limitation of electrochemical capacitors is their low energy density and for this reason, there is widespread interest in pseudocapacitive materials that use Faradaic reactions to store charge. One candidate pseudocapacitive material is orthorhombic MoO3 (α-MoO3), a layered compound with a high theoretical capacity for lithium (279 mA h g-1 or 1,005 C g-1). Here, we report on the properties of reduced α-MoO3-x(R-MoO3-x) and compare it with fully oxidized α-MoO3 (F-MoO3). The introduction of oxygen vacancies leads to a larger interlayer spacing that promotes faster charge storage kinetics and enables the α-MoO3 structure to be retained during the insertion and removal of Li ions. The higher specific capacity of the R-MoO3-x is attributed to the reversible formation of a significant amount of Mo4+ following lithiation. This study underscores the potential importance of incorporating oxygen vacancies into transition metal oxides as a strategy for increasing the charge storage kinetics of redox-active materials.

Compressed plane waves yield a compactly supported multiresolution basis for the Laplace operator.

This paper describes an L1 regularized variational framework for developing a spatially localized basis, compressed plane waves, that spans the eigenspace of a differential operator, for instance, the Laplace operator. Our approach generalizes the concept of plane waves to an orthogonal real-space basis with multiresolution capabilities.

Ultralow Thermal Conductivity in Full Heusler Semiconductors.

Semiconducting half and, to a lesser extent, full Heusler compounds are promising thermoelectric materials due to their compelling electronic properties with large power factors. However, intrinsically high thermal conductivity resulting in a limited thermoelectric efficiency has so far impeded their widespread use in practical applications. Here, we report the computational discovery of a class of hitherto unknown stable semiconducting full Heusler compounds with ten valence electrons (X_{2}YZ, X=Ca, Sr, and Ba; Y=Au and Hg; Z=Sn, Pb, As, Sb, and Bi) through high-throughput ab initio screening. These new compounds exhibit ultralow lattice thermal conductivity κ_{L} close to the theoretical minimum due to strong anharmonic rattling of the heavy noble metals, while preserving high power factors, thus resulting in excellent phonon-glass electron-crystal materials.

Compressed modes for variational problems in mathematics and physics.

This article describes a general formalism for obtaining spatially localized ("sparse") solutions to a class of problems in mathematical physics, which can be recast as variational optimization problems, such as the important case of Schrödinger's equation in quantum mechanics. Sparsity is achieved by adding an regularization term to the variational principle, which is shown to yield solutions with compact support ("compressed modes"). Linear combinations of these modes approximate the eigenvalue spectrum and eigenfunctions in a systematically improvable manner, and the localization properties of compressed modes make them an attractive choice for use with efficient numerical algorithms that scale linearly with the problem size.

Ruthenia-based electrochemical supercapacitors: insights from first-principles calculations.

Electrochemical supercapacitors (ECs) have important applications in areas wherethe need for fast charging rates and high energy density intersect, including in hybrid and electric vehicles, consumer electronics, solar cell based devices, and other technologies. In contrast to carbon-based supercapacitors, where energy is stored in the electrochemical double-layer at the electrode/electrolyte interface, ECs involve reversible faradaic ion intercalation into the electrode material. However, this intercalation does not lead to phase change. As a result, ECs can be charged and discharged for thousands of cycles without loss of capacity. ECs based on hydrous ruthenia, RuO2·xH2O, exhibit some of the highest specific capacitances attained in real devices. Although RuO2 is too expensive for widespread practical use, chemists have long used it as a model material for investigating the fundamental mechanisms of electrochemical supercapacitance and heterogeneous catalysis. In this Account, we discuss progress in first-principles density-functional theory (DFT) based studies of the electronic structure, thermodynamics, and kinetics of hydrous and anhydrous RuO2. We find that DFT correctly reproduces the metallic character of the RuO2 band structure. In addition, electron-proton double-insertion into bulk RuO2 leads to the formation of a polar covalent O-H bond with a fractional increase of the Ru charge in delocalized d-band states by only 0.3 electrons. This is in slight conflict with the common assumption of a Ru valence change from Ru(4+) to Ru(3+). Using the prototype electrostatic ground state (PEGS) search method, we predict a crystalline RuOOH compound with a formation energy of only 0.15 eV per proton. The calculated voltage for the onset of bulk proton insertion in the dilute limit is only 0.1 V with respect to the reversible hydrogen electrode (RHE), in reasonable agreement with the 0.4 V threshold for a large diffusion-limited contribution measured experimentally. DFT calculations also predict that proton diffusion in RuO2 is hindered by a migration barrier of 0.8 eV, qualitatively explaining the observed strong charging rate-dependence of the diffusion-limited contribution. We found that reversible adsorption of up to 1.5 protons per Ru on the (110) surface contributes to the measured capacitive current at higher voltages. PEGS-derived models of the crystal structure of hydrated ruthenia show that incorporation of water in Ru vacancies or in bulk crystals is energetically much more costly than segregation of water molecules between slabs of crystalline RuO2. These results lend support to the so-called "water at grain boundaries" model for the structure of hydrous RuO2·xH2O. This occurs where metallic nanocrystals of RuO2 are separated by grain boundary regions filled with water molecules. Chemists have attributed the superior charge storage properties of hydrous ruthenia to the resulting composite structure. This facilitates fast electronic transport through the metallic RuO2 nanocrystals and fast protonic transport through the regions of structural water at grain boundaries.

Lattice anharmonicity and thermal conductivity from compressive sensing of first-principles calculations.

First-principles prediction of lattice thermal conductivity κ(L) of strongly anharmonic crystals is a long-standing challenge in solid-state physics. Making use of recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics. Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Nonintuitively, high accuracy is achieved when the model is trained on first-principles forces in quasirandom atomic configurations. The method is demonstrated for Si, NaCl, and Cu(12)Sb(4)S(13), an earth-abundant thermoelectric with strong phonon-phonon interactions that limit the room-temperature κ(L) to values near the amorphous limit.

Facet-selective adsorption on noble metal crystals guided by electrostatic potential surfaces of aromatic molecules.

We aim to provide a model platform composed of aromatic molecules and noble metal surfaces to study the molecular facet-selective adsorption and employ the discoveries to design surfactants for predictable shape-controlled syntheses of nanocrystals. Starting from Pt, it is demonstrated that negative electrostatic potential on the aromatic ring is the prerequisite to display binding selectivity to Pt(111), while a neutral to positive one prefers Pt(100). The geometric matching between molecular binding sites and surface lattices plays a role as well in facet selectivity. Significantly, Raman spectroscopy has been employed to probe the interactions between aromatic molecules and metal surfaces, providing direct evidence of their binding mechanisms. These discoveries are further exploited to design and identify Pd(111) and Pd(100) facet-specific surfactants. These results represent a step forward in achieving predictable and programmable nanostructures through better understanding of organic-inorganic interfaces.

Electronic structures of an epitaxial graphene monolayer on SiC(0001) after gold intercalation: a first-principles study.

The atomic and electronic structures of an Au-intercalated graphene monolayer on the SiC(0001) surface were investigated using first-principles calculations. The unique Dirac cone of graphene near the K point reappeared as the monolayer was intercalated by Au atoms. Coherent interfaces were used to study the mismatch and the strain at the boundaries. Our calculations showed that the strain at the graphene/Au and Au/SiC(0001) interfaces also played a key role in the electronic structures. Furthermore, we found that at an Au coverage of 3/8 ML, Au intercalation leads to a strong n-type doping of graphene. At 9/8 ML, it exhibited a weak p-type doping, indicative that graphene was not fully decoupled from the substrate. The shift in the Dirac point resulting from the electronic doping was not only due to the different electronegativities but also due to the strain at the interfaces. Our calculated positions of the Dirac points are consistent with those observed in the ARPES experiment (Gierz et al 2010 Phys. Rev. B 81 235408).

Vacancy-mediated dehydrogenation of sodium alanate.

Clarification of the mechanisms of hydrogen release and uptake in transition-metal-doped sodium alanate, NaAlH(4), a prototypical high-density complex hydride, has fundamental importance for the development of improved hydrogen-storage materials. In this and most other modern hydrogen-storage materials, H(2) release and uptake are accompanied by long-range diffusion of metal species. Using first-principles density-functional theory calculations, we have determined that the activation energy for Al mass transport via AlH(3) vacancies is Q = 85 kJ/mol.H(2), which is in excellent agreement with experimentally measured activation energies in Ti-catalyzed NaAlH(4). The activation energy for an alternate decomposition mechanism via NaH vacancies is found to be significantly higher: Q = 112 kJ/mol.H(2). Our results suggest that bulk diffusion of Al species is the rate-limiting step in the dehydrogenation of Ti-doped samples of NaAlH(4) and that the much higher activation energies measured for uncatalyzed samples are controlled by other processes, such as breaking up of AlH(4)(-) complexes, formation/dissociation of H(2) molecules, and/or nucleation of the product phases.

Designing chemical analogs to PbTe with intrinsic high band degeneracy and low lattice thermal conductivity.

High-efficiency thermoelectric materials require simultaneously high power factors and low thermal conductivities. Aligning band extrema to achieve high band degeneracy, as realized in PbTe, is one of the most efficient approaches to enhance power factor. However, this approach usually relies on band structure engineering, e.g., via chemical doping or strain. By employing first-principles methods with explicit computation of phonon and carrier lifetimes, here we show two full-Heusler compounds Li2TlBi and Li2InBi have exceptionally high power factors and low lattice thermal conductivities at room temperature. The expanded rock-salt sublattice of these compounds shifts the valence band maximum to the middle of the Σ line, increasing the band degeneracy by a factor of three. Meanwhile, resonant bonding in the PbTe-like sublattice and soft Tl-Bi (In-Bi) bonding interaction is responsible for intrinsic low lattice thermal conductivities. Our results present an alternative strategy of designing high performance thermoelectric materials.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce4+/Ce3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

First-principles calculated decomposition pathways for LiBH4 nanoclusters.

We analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found that the bulk material decomposes into LiH and B, with Li2B12H12 as a kinetically inhibited intermediate phase, (LiBH4)n nanoclusters with n ≤ 12 are predicted to decompose into mixed LinBn clusters via a series of intermediate clusters of LinBnHm (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.

Scalable solution-phase epitaxial growth of symmetry-mismatched heterostructures on two-dimensional crystal soft template.

Epitaxial heterostructures with precisely controlled composition and electronic modulation are of central importance for electronics, optoelectronics, thermoelectrics, and catalysis. In general, epitaxial material growth requires identical or nearly identical crystal structures with small misfit in lattice symmetry and parameters and is typically achieved by vapor-phase depositions in vacuum. We report a scalable solution-phase growth of symmetry-mismatched PbSe/Bi2Se3 epitaxial heterostructures by using two-dimensional (2D) Bi2Se3 nanoplates as soft templates. The dangling bond-free surface of 2D Bi2Se3 nanoplates guides the growth of PbSe crystal without requiring a one-to-one match in the atomic structure, which exerts minimal restriction on the epitaxial layer. With a layered structure and weak van der Waals interlayer interaction, the interface layer in the 2D Bi2Se3 nanoplates can deform to accommodate incoming layer, thus functioning as a soft template for symmetry-mismatched epitaxial growth of cubic PbSe crystal on rhombohedral Bi2Se3 nanoplates. We show that a solution chemistry approach can be readily used for the synthesis of gram-scale PbSe/Bi2Se3 epitaxial heterostructures, in which the square PbSe (001) layer forms on the trigonal/hexagonal (0001) plane of Bi2Se3 nanoplates. We further show that the resulted PbSe/Bi2Se3 heterostructures can be readily processed into bulk pellet with considerably suppressed thermal conductivity (0.30 W/m·K at room temperature) while retaining respectable electrical conductivity, together delivering a thermoelectric figure of merit ZT three times higher than that of the pristine Bi2Se3 nanoplates at 575 K. Our study demonstrates a unique epitaxy mode enabled by the 2D nanocrystal soft template via an affordable and scalable solution chemistry approach. It opens up new opportunities for the creation of diverse epitaxial heterostructures with highly disparate structures and functions.

Physics of bandgap formation in Cu-Sb-Se based novel thermoelectrics: the role of Sb valency and Cu d levels.

In this paper we discuss the results of ab initio electronic structure calculations for Cu(3)SbSe(4) (Se4) and Cu(3)SbSe(3) (Se3), two narrow bandgap semiconductors of thermoelectric interest. We find that Sb is trivalent in both the compounds, in contrast to a simple nominal valence (ionic) picture which suggests that Sb should be 5 + in Se4. The gap formation in Se4 is quite subtle, with hybridization between Sb 5s and the neighboring Se 4s, 4p orbitals, position of Cu d states, and non-local exchange interaction, each playing significant roles. Thermopower calculations show that Se4 is a better p-type system. Our theoretical results for Se4 agree very well with recent experimental results obtained by Skoug et al (2011 Sci. Adv. Mater. 3 602).

Trans-interface diffusion-controlled coarsening.

Accurate theoretical predictions of the volume-fraction dependence during diffusion-controlled coarsening of a polydisperse assembly of particles have proved difficult. Here, a new model of coarsening is presented, involving diffusive transport through the coherent interface between ordered and disordered phases, which atomistic calculations show has a ragged structure. The interface is a diffusion bottleneck when the ordered phase is dispersed. It is predicted that the square of the average radius grows linearly with time, that the depletion of solute decreases as the inverse square-root of time, and that there is no effect of volume fraction on kinetics and the scaled particle-size distributions. These differ dramatically from predictions of modern theories of diffusion-controlled coarsening. Data on coarsening in Ni-Al alloys is examined. We show that no other theory is consistent with the experimentally observed absence of an effect of volume fraction on coarsening of ordered gamma' (Ni3Al) precipitates in a disordered Ni-Al (gamma) matrix, and the strong volume-fraction dependence of coarsening of gamma precipitates in an ordered gamma' matrix.