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The x-ray restrained wave function (XRW) method is a quantum crystallographic technique to extract wave functions compatible with experimental x-ray diffraction data. The approach looks for wave functions that minimize the energies of the investigated systems and also reproduce sets of x-ray structure factors. Given the strict relationship between x-ray structure factors and electron distributions, the strategy practically allows determining wave functions that correspond to given (usually experimental) electron densities. In this work, the capabilities of the XRW approach were further tested. The aim was to evaluate whether the XRW technique could serve as a tool for suggesting new exchange-correlation functionals for density functional theory or refining existing ones. Additionally, the ability of the method to address the influences of the crystalline environment was also assessed. The outcomes of XRW computations were thus compared to those of traditional gas-phase, embedding quantum mechanics/molecular mechanics, and fully periodic calculations. The results revealed that, irrespective of the initial conditions, the XRW computations practically yield a consensus electron density, in contrast to the currently employed density functional approximations (DFAs), which tend to give a too large range of electron distributions. This is encouraging in view of exploiting the XRW technique to develop improved functionals. Conversely, the calculations also emphasized that the XRW method is limited in its ability to effectively address the influences of the crystalline environment. This underscores the need for a periodic XRW technique, which would allow further untangling the shortcomings of DFAs from those inherent to the XRW approach. [ABSTRACT FROM AUTHOR]

The monoclinic (In 0.25 Al 0.75) 2 O 3 alloy has been suggested as an ideal material to create monoclinic Ga 2 O 3 heterostructures, as it provides a close lattice match to β - Ga 2 O 3 along with a 1 eV conduction-band offset. Achieving intentional n -type doping in Ga 2 O 3 heterostructures is important for device applications, but this may be difficult due to the high Al content of this alloy. Here, we use density functional theory with a hybrid functional to investigate common donor dopants, in particular, Si, Sn, C, and Ge substituting on cation sites, and H interstitials, in In 2 O 3 and InAlO 3. We identify Si as the optimal donor, as it is a shallow donor for In concentrations above 14%. Its formation energy is also low, indicating that these donors will incorporate during growth. For higher In concentrations, Sn (above 33% In) and Ge (above 35% In) are also promising donors, with Sn having comparable formation energies to Si. [ABSTRACT FROM AUTHOR]

The effects of carbon in heavily phosphorus-doped Czochralski (HP-Cz) silicon (Si) substrates, with the concentrations across an order of magnitude from 1016 to 1017 cm−3, on the out-diffusion of phosphorus impurities within n/n+ epitaxial Si (Epi-Si) wafers have been investigated. It is found that the increase in the carbon concentration ([C]) from 1.0 × 1016 to 1.0 × 1017 cm−3 leads to the enhanced phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1100 °C in an N2 or an O2 ambient or to anneal at 1150 °C in an N2 ambient, but hardly affects the phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1150 °C in an O2 ambient. Based on the density functional theory calculations, it is derived that the increase in the [C] from 1.0 × 1016 to 1.0 × 1017 cm−3 in the HP-Cz Si substrate results in a significantly increased thermal equilibrium concentration of self-interstitial silicon (SiI) atoms at 1100 or 1150 °C, which, in turn, leads to the increased concentration of the SiI atoms that out-diffuse from the substrate to the epitaxial layer because the SiI atoms diffuse extremely fast in Si. Such a carbon-induced increase in the concentration of SiI atoms is believed to be responsible for the aforementioned enhanced phosphorus out-diffusion, which is predominantly dictated by the interstitialcy mechanism. In the case of anneal in the O2 ambient at sufficiently high temperatures such as 1150 °C, a large number of excessive SiI atoms injected into the Epi-Si wafer substantially mask the carbon enhancement effect on the phosphorus out-diffusion. Of technological significance, it is deduced that the [C] should be not higher than 1.0 × 1016 cm−3 in the HP-Cz Si wafers as the substrates of n/n+ Epi-Si wafers used for power devices. [ABSTRACT FROM AUTHOR]

Investigating the interplay between charge and spin conversion in two-dimensional (2D) materials holds significant promise for futuristic electronic applications. Through density functional theory, our study delves into the charge-spin conversion and spin density dynamics in the non-magnetic SnNBr monolayer under time-reversal invariance. The breaking of out-of-plane mirror symmetry and inversion symmetry, along with the presence of spin–orbit coupling (SOC) lead to a notable momentum-dependent spin band splitting or Rashba effect induced by the inherent out-of-plane electric field. Theoretical calculations reveal not only the presence of profound Rashba spin splitting but also the coexistence of intrinsic spin Hall effects in the SnNBr monolayer. Analysis of k-resolved spin Berry curvature sheds light on the origin of the substantial intrinsic spin Hall conductivity. Furthermore, our research highlights the modulation of charge-to-spin conversion and spin density accumulation through in-plane biaxial strains. Moreover, the variation in the Rashba parameter is correlated with the changes in the built-in out-of-plane electric field and microscopic atomic orbital contributions. These findings underscore the exceptional potential of the non-centrosymmetric SnNBr monolayer for advanced spintronics, spin-orbitronics, and piezo-spintronic applications, and serve as a catalyst for further experimental investigations. [ABSTRACT FROM AUTHOR]

The accuracy of orbital-free density functional theory depends on the approximations made for a Kinetic Energy (KE) functional. Until now, the most accurate KEDFs are based on non-local kernels constructed from the linear response theory of homogeneous electron gas. In this work, we explore beyond the HEG by employing a more general kernel based on the jellium-with-gap model (JGM). The proposed functional incorporates several new features, such as (i) having the correct low momentum(q) limit of the response function for metals and semiconductors without any modeling term, (ii) the underlying kernel is density-independent, and most importantly, (iii) parameter-free. The accuracy and efficiency of the proposed JGM NL-KEDF have been demonstrated for several semiconductors and metals. The encouraging results indicate the utility and predictive power of the JGM kernel for NL KEDF developments. This approach is also physically appealing and practically useful as we have presented a general formalism to incorporate the gap kernel in all existing Lindhard-based functionals. [ABSTRACT FROM AUTHOR]

A new combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian parameterized solely using the benchmark ab initio vertical excitation energies obtained from the QUEST databases is presented. This new formulation differs from all previous versions of the method in that the choice of the underlying exchange–correlation (XC) functional employed to construct the one-particle (orbital) basis is considered, and a new XC functional, QTP17, is chosen for its ability to generate a balanced description of core and valence vertical excitation energies. The ability of the new DFT/MRCI Hamiltonian, termed QE8, to furnish accurate excitation energies is confirmed using benchmark quantum chemistry computations, and a mean absolute error of 0.16 eV is determined for the wide range of electronic excitations included in the validation dataset. In particular, the QE8 Hamiltonian dramatically improves the performance of DFT/MRCI for doubly excited states. The performance of fast approximate DFT/MRCI methods, p-DFT/MRCI and DFT/MRCI(2), is also evaluated using the QE8 Hamiltonian, and they are found to yield excitation energies in quantitative agreement with the parent DFT/MRCI method, with the two methods exhibiting a mean difference of 0.01 eV with respect to DFT/MRCI over the entire benchmark set. [ABSTRACT FROM AUTHOR]

The stability of a mixture of two different surface reconstructions is investigated focusing on GaN(0001) surface mixed with Ga a d (2 × 2) and 3Ga-H(2 × 2) domains using the density functional theory calculations. Since the number of candidate structures is enormous, the structures sampled by Bayesian optimization are analyzed. As a result, the local electron counting (EC) rule alone was found to be insufficient to explain such stability. Then, augmenting the EC rule, a data-driven Ising model is proposed. The model allows the evaluation of the whole enormous number of candidate structures. The approach is expected to be useful for theoretical studies of such mixtures on various semiconductor surfaces. [ABSTRACT FROM AUTHOR]

We find that the unit cell volume (V), which affects many properties, decreases too rapidly with strain when calculated with standard density functional theories (DFTs) such as local density approximation (LDA). We find that this demerit is moderated with the use of the Hubbard potential U for local electron correlation (DFT + U). However, the introduction of U to standard DFTs, e.g., LDA and Perdew–Burke–Ernzerhof functional (PBE) optimized for solids (PBEsol), leads to the excessive underestimation of the spontaneous polarization (PS) and frequently extinguishes PS. Therefore, we attempt to improve the overall accuracy of DFTs for ferroelectrics by using U in several DFT methods including PBE that overestimates PS and lattice constants. We demonstrate that PBE with U (PBE + U) is in excellent agreement with the experimental properties of BaTiO3 and SrTiO3, with improvements in the estimates of lattice constants, PS, the phonon frequency, the antiferrodistortive angle of 105 K-phase SrTiO3, the bandgap, the strain dependence of V, and hole polarons. When the lattice parameters and PS moderately agree with the experimental data, PBE + U with a single U set can produce both electron and hole polarons. Hence, PBE + U can be a practical substitute of hybrid functionals for perovskite oxide ferroelectrics, except for the estimation of the bandgap. Furthermore, we propose an approach to construct a functional accurately depicting the incipient ferroelectric state of SrTiO3. Additionally, these results suggest that conventional DFT underestimates PS under compressive in-plane strain and predicts the unrealistic deformation of ferroelectrics and that in-plane-strained lattices can mitigate the problems associated with U. [ABSTRACT FROM AUTHOR]

Field emission is an important process with a variety of applications. Quantitative predictions of such electron emission need to include details of the internal potentials that shape the electronic wavefunctions (and hence the tunneling probability), predictive analysis of the work function barrier (ΦB), and knowledge of the electron distribution at the surface that constitutes the supply function. Here, these various factors were all collectively considered based on a combined Monte Carlo-density functional theory approach. Results were obtained for both the field-dependent cold electron emission current density as well as photoemission from a short laser pulse. The method also allows for calculations of field-dependent emittance. The technique is general and could be extended to include plasmon–polariton modes, different thicknesses of coatings, and role of surface adsorbates and defects. [ABSTRACT FROM AUTHOR]

Surface-specific sum frequency generation vibrational spectroscopy is applied to study the molecular configuration of short-chain n-alkanethiol self-assembled monolayers (SAMs with n = 2–6) on the Au surface. For monolayers with n ≥ 3, the alkanethiols are upright-oriented, with the CH3 tilt angle varying between ∼33° and ∼46° in clear even–odd dependency. The ethanethiol monolayer (n = 2) is, however, found to exhibit a distinct lying-down configuration with a larger methyl tilt angle (67°–79°) and a smaller CH2 tilt angle (56°–68°). Such a unique configurational transition from n = 2 to n ≥ 3 discloses the steric effect owing to chain–chain interaction among neighboring molecules. Through density functional theory calculations, the transition is further confirmed to be energetically favorable for thiols on a defective reconstructed Au(111) surface but not on the pristine one. Our study highlights the roles of the chain–chain interaction and the substrate surface atomic structure when organizing SAMs, offering a strategic pathway for exploiting their applications. [ABSTRACT FROM AUTHOR]

Density functional theory was employed to examine the adsorption and thermal evolution of nitrogen species on diamond(111) impacted by microwave N2 plasma. On bare domains of diamond, as represented by the models of C(111)-2 × 1 and graphite-like C(111), N2(ad) is identified as the major surface species; the desorption of N2(ad) proceeds on both models via a concerted process of breaking two C–N bonds. By contrast, there is evidence of the formation of (NH)2(ad) via the insertion reaction of microwave N2 plasma on hydrogenated domains of diamond, as represented by the models of C(111)-2 × 1-H and C(111)-1 × 1-H. Interestingly, contrasting dynamics of desorption of (NH)2(ad) are presented on these two models, that is, via sequential breaking of two C–N bonds on C(111)-2 × 1-H and via concerted breaking of both C–N bonds on C(111)-1 × 1-H. Our results demonstrate that the observed diversity of surface nitrogen species in composition, bonding, vibration, and desorption in prior experiments is linked to domains of a variety of surface terminations and reconstructions on diamond(111). [ABSTRACT FROM AUTHOR]

The interplay between orientation transition and chiral self-assemblies of para-terphenyl (P3P) molecules on the Cd(0001) surface has been investigated using low temperature scanning tunneling microscopy and density functional theory calculations. Three distinct molecular orientations have been discerned from the self-assembled thin films of P3P. At the low coverage, flat-lying molecules appear in the homochiral domains with the incommensurate registry to the substrate. With the coverage increasing, the incoming molecules are incorporated into the first layer with edge-on orientation and form the self-assembled zigzag chains. The alternative arrangement of zigzag chains with opposite chirality leads to the formation of a c(4 × 2) superstructure, in which the tilted molecules exhibit orientational frustration and fuzzy noises. The analysis of the tunneling spectra reveals that the electronic structure of P3P layers is contingent upon the hybridization between the electronic states of P3P molecules and the Cd(0001) surface. These results provide important insights into the interplay between orientational transition and chiral assembly of P3P molecules on metal substrates. [ABSTRACT FROM AUTHOR]

Density Functional Theory (DFT) has become a cornerstone in the modeling of metals. However, accurately simulating metals, particularly under extreme conditions, presents two significant challenges. First, simulating complex metallic systems at low electron temperatures is difficult due to their highly delocalized density matrix. Second, modeling metallic warm-dense materials at very high electron temperatures is challenging because it requires the computation of a large number of partially occupied orbitals. This study demonstrates that both challenges can be effectively addressed using the latest advances in linear-scaling stochastic DFT methodologies. Despite the inherent introduction of noise into all computed properties by stochastic DFT, this research evaluates the efficacy of various noise reduction techniques under different thermal conditions. Our observations indicate that the effectiveness of noise reduction strategies varies significantly with the electron temperature. Furthermore, we provide evidence that the computational cost of stochastic DFT methods scales linearly with system size for metal systems, regardless of the electron temperature regime. [ABSTRACT FROM AUTHOR]

The superadiabatic dynamical density functional theory (superadiabatic-DDFT) is a promising new method for the study of colloidal systems out-of-equilibrium. Within this approach, the viscous forces arising from interparticle interactions are accounted for in a natural way by explicitly treating the dynamics of the two-body correlations. For bulk systems subject to spatially homogeneous shear, we use the superadiabatic-DDFT framework to calculate the steady-state pair distribution function and the corresponding viscosity for low values of the shear-rate. We then consider a variant of the central approximation underlying this superadiabatic theory and obtain an inhomogeneous generalization of a rheological bulk theory due to Russel and Gast. This paper thus establishes for the first time a connection between DDFT approaches, formulated to treat inhomogeneous systems, and existing work addressing nonequilibrium microstructure and rheology in bulk colloidal suspensions. [ABSTRACT FROM AUTHOR]

Lennard-Jones potential parameters have been determined for the interlayered interaction in 12 elemental layered crystals. The layered crystals include corrugated borophene, buckled honeycomb structures with elements from the group IV (Si, Ge, and Sn) and group V (P, As, Sb, and Bi), as well as four puckered structures in the aw-phase (Sb and Bi) and sw-phase (P and As). We first calculated the minimal interfacial energy and the interlayer equilibrium distance for two typical shifted stackings, AA and AB, for every bilayer crystal using the density functional theory with a long-range dispersion correction. Then, we use the Lennard-Jones potential and the corresponding derivative to graphically match the calculated adhesion energy and the zero resultant force along the out-of-plane direction, determining the energy parameter and the size parameter for both stackings. The Lennard-Jones model with the obtained parameters can be in good agreement with the first-principles calculations for the AA and AB stackings in describing the relationship between the interfacial energy and the interlayer distance, and the Lennard-Jones parameters for the other stackings are directly determined according to Lorentz–Berthelot combining rules. The parameters can be applied in molecular dynamics simulations for the interfacial effect of elemental layered materials such as mechanical peeling and interlayer friction, as well as stacking formation, and the analytical method can be extended to determine the parameters of the Lennard-Jones potential for the compound layered crystals and the interlayer heterojunction structures. [ABSTRACT FROM AUTHOR]

Given the extensive use of fluorination in molecular design, it is imperative to understand the solvation properties of fluorinated compounds and the impact of the C–F bond on electrostatic interactions. Vibrational spectroscopy can provide direct insights into these interactions by using the C–F bond stretching [v(C–F)] as an electric field probe through the vibrational Stark effect (VSE). In this work, we explore the VSE of the three basic patterns of aliphatic fluorination, i.e., mono-, di-, and trifluorination in CF, CF2, and CF3 groups, respectively, and compare their response to the well-studied aromatic v(C–F). Magnitudes (i.e., Stark tuning rates) and orientations of the difference dipole vectors of the v(C–F)-containing normal modes were determined using density functional theory and a molecular dynamics (MD)-assisted solvatochromic analysis of model compounds in solvents of varying polarity. We obtain Stark tuning rates of 0.2–0.8 cm−1/(MV/cm), with smallest and largest electric field sensitivities for CFaliphatic and CF3,aliphatic, respectively. While average electric fields of solvation were oriented along the main symmetry axis of the CFn, and thus along its static dipole, the Stark tuning rate vectors were tilted by up to 87° potentially enabling to map electrostatics in multiple dimensions. We discuss the influence of conformational heterogeneity on spectral shifts and point out the importance of multipolar and/or polarizable MD force fields to describe the electrostatics of fluorinated molecules. The implications of this work are of direct relevance for studies of fluorinated molecules as found in pharmaceuticals, fluorinated peptides, and proteins. [ABSTRACT FROM AUTHOR]

Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O–H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]− and [Ni3(EtOH)]− clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]− cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules. [ABSTRACT FROM AUTHOR]

In this paper, benchmark results are presented on the calculation of vertical electronic excitation energies using a long-range second-order polarization propagator approximation (SOPPA) description with a short-range density functional theory description based on the Perdew–Burke–Ernzerhof (PBE) functional. The excitation energies are investigated for 132 singlet states and 71 triplet states across 28 medium-sized organic molecules. The results show that overall SOPPA-srPBE always performs better than PBE and that SOPPA-srPBE performs better than SOPPA for singlet states, but slightly worse than SOPPA for triplet states when CC3 results are the reference values. [ABSTRACT FROM AUTHOR]

The ultra-wide bandgap of gallium oxide provides a rich plethora of electrically active defects. Understanding and controlling such defects is of crucial importance in mature device processing. Deep-level transient spectroscopy is one of the most sensitive techniques for measuring electrically active defects in semiconductors and, hence, a key technique for progress toward gallium oxide-based components, including Schottky barrier diodes and field-effect transistors. However, deep-level transient spectroscopy does not provide chemical or configurational information about the defect signature and must, therefore, be combined with other experimental techniques or theoretical modeling to gain a deeper understanding of the defect physics. Here, we discuss the current status regarding the identification of electrically active defects in beta-phase gallium oxide, as observed by deep-level transient spectroscopy and supported by first-principles defect calculations based on the density functional theory. We also discuss the coordinated use of the experiment and theory as a powerful approach for studying electrically active defects and highlight some of the interesting but challenging issues related to the characterization and control of defects in this fascinating material. [ABSTRACT FROM AUTHOR]

Using the density functional theory, we conducted a study on the electrification upon contact between hydrophobic liquid molecules and water molecules, revealing localized characteristics of contact-electrification. These "localized features" refer to the specific microscale characteristics where electron transfer predominantly occurs at the contact regions, influenced by factors such as atomic distances and molecular orientations. Although the electrostatic potential and the highest occupied molecular orbital–lowest unoccupied molecular orbital gap offer substantial predictive insights for electron transfer across polymer interfaces, they fall short in capturing the complexities associated with the interaction between hydrophobic liquids and water molecules. The electronegativity of elements at the interface and the localization of molecular orbitals play a decisive role in electron transfer. Simultaneously, for liquid molecules with irregular structures, there is no correlation between the "contact area" and the amount of electron transfer. The "contact area" refers to the surface region where two different liquid molecules come into close proximity. It is defined by the surface area of atoms with interatomic distances smaller than the van der Waals radius. This study challenges traditional assumptions about contact-electrification, particularly in liquid–liquid interfaces, providing new insights into the localized nature of this phenomenon. [ABSTRACT FROM AUTHOR]

We report a theoretical investigation of temperature, size, and composition effects on the structural, energetic, and electronic properties of the (La4O6)n, (La2Ce2O7)n, and (Ce4O8)n nanoclusters (NCs) for n = 10, 18. Furthermore, we investigated the single O vacancy formation energy as a function of the geometric location within the NC. Our calculations are based on the combination of force-field molecular dynamics (MD) simulations and density functional theory calculations. We identified a phase transition from disordered to ordered structures for all NCs via MD simulations and structural analysis, e.g., radius changes, radial distribution function, common neighbor analysis, etc. The transition is sharp for La36Ce36O126, La20Ce20O70, and Ce72O144 due to the crystalline domains in the core and less abrupt for Ce40O80, La40O60, and La72O108. As expected, radius changes are abrupt at the transition temperature, as are morphological differences between NCs located below and above the transition temperature. We found a strong dependence on the O vacancy formation energy (Evac) and its location within the NCs. For example, for La40O60, Evac decreases almost linearly as the distance from the geometric center increases; however, the same trend was not observed for Ce40O80, while there are large deviations from the linear trend for La20Ce20O70. Evac has smaller values for Ce40O80 and higher values for La40O60, that is, almost three times, while Evac has intermediate values for mixed oxides, as expected from weighted averages. Therefore, the mixture of one formula unit of La2O3 with two formula units of CeO2 has the effect of increasing the stability of CeO2 (binding energy), which increases the magnitude of the formation energy of the O vacancy. [ABSTRACT FROM AUTHOR]

Spin–orbit coupling induces a current density in the ground state, which consequently requires a generalization for meta-generalized gradient approximations. That is, the exchange–correlation energy has to be constructed as an explicit functional of the current density, and a generalized kinetic energy density has to be formed to satisfy theoretical constraints. Herein, we generalize our previously presented formalism of spin–orbit current density functional theory [Holzer et al., J. Chem. Phys. 157, 204102 (2022)] to non-magnetic and magnetic periodic systems of arbitrary dimension. In addition to the ground-state exchange–correlation potential, analytical derivatives such as geometry gradients and stress tensors are implemented. The importance of the current density is assessed for band gaps, lattice constants, magnetic transitions, and Rashba splittings. In the latter, the impact of the current density may be larger than the deviation between different density functional approximations. [ABSTRACT FROM AUTHOR]

We present an exchange–correlation approximation in which the Coulomb interaction is split into long- and short-range components and the range separation is determined by a non-empirical density functional. The functional respects important constraints, such as the homogeneous and slowly varying density limits, leads to the correct long-range potential, and eliminates one-electron self-interaction. Our approach is designed for spectroscopic purposes and closely approximates the piecewise linearity of the energy as a function of the particle number. The functional's accuracy for predicting the fundamental gap in generalized Kohn–Sham theory is demonstrated for a large number of systems, including organic semiconductors with a notoriously difficult electronic structure. [ABSTRACT FROM AUTHOR]

The discovery of advanced thermal materials with exceptional phonon properties drives technological advancements, impacting innovations from electronics to superconductors. Understanding the intricate relationship between composition, structure, and phonon thermal transport properties is crucial for speeding up such discovery. Exploring innovative materials involves navigating vast design spaces and considering chemical and structural factors on multiple scales and modalities. Artificial intelligence (AI) is transforming science and engineering and poised to transform discovery and innovation. This era offers a unique opportunity to establish a new paradigm for the discovery of advanced materials by leveraging databases, simulations, and accumulated knowledge, venturing into experimental frontiers, and incorporating cutting-edge AI technologies. In this perspective, first, the general approach of density functional theory (DFT) coupled with phonon Boltzmann transport equation (BTE) for predicting comprehensive phonon properties will be reviewed. Then, to circumvent the extremely computationally demanding DFT + BTE approach, some early studies and progress of deploying AI/machine learning (ML) models to phonon thermal transport in the context of structure–phonon property relationship prediction will be presented, and their limitations will also be discussed. Finally, a summary of current challenges and an outlook of future trends will be given. Further development of incorporating AI/ML algorithms for phonon thermal transport could range from phonon database construction to universal machine learning potential training, to inverse design of materials with target phonon properties and to extend ML models beyond traditional phonons. [ABSTRACT FROM AUTHOR]

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations. [ABSTRACT FROM AUTHOR]

We present dynamic density functional theory (DDFT) incorporating general inhomogeneous, incompressible, time-dependent background flows and inertia, describing externally driven passive colloidal systems out of equilibrium. We start by considering the underlying nonequilibrium Langevin dynamics, including the effect of the local velocity of the surrounding liquid bath, to obtain the nonlinear, nonlocal partial differential equations governing the evolution of the (coarse-grained) density and velocity fields describing the dynamics of colloids. In addition, we show both with heuristic arguments, and by numerical solution, that our equations and solutions agree with existing DDFTs in the overdamped (high friction) limit. We provide numerical solutions that model the flow of hard spheres, in both unbounded and confined domains, and compare with previously derived DDFTs with and without the background flow. [ABSTRACT FROM AUTHOR]

Ge-Sb-Te (GST) alloys are leading phase-change materials for data storage due to the fast phase transition between amorphous and crystalline states. Ongoing research aims at improving the stability of the amorphous phase to improve retention. This can be accomplished by the introduction of carbon as a dopant to Ge2Sb2Te5, which is known to alter the short- and mid-range structure of the amorphous phase and form covalently bonded C clusters, both of which hinder crystallization. The relative importance of these processes as a function of C concentration is not known. We used molecular dynamics simulation based on density functional theory to study how carbon doping affects the atomic structure of GST-C. Carbon doping results in an increase in tetrahedral coordination, especially of Ge atoms, and this is known to stabilize the amorphous phase. We observe an unexpected, non-monotonous trend in the number of tetrahedral bonded Ge with the amount of carbon doping. Our simulations show an increase in the number of tetrahedral bonded Ge up to 5 at.% C, after which the number saturates and begins to decrease above 14 at.% C. The carbon atoms aggregate into clusters, mostly in the form of chains and graphene flakes, leaving less carbon to disrupt the GST matrix at higher carbon concentrations. Different degrees of carbon clustering can explain divergent experimental results for recrystallization temperature for carbon doped GST. [ABSTRACT FROM AUTHOR]

We present a comprehensive investigation into the dissociative chemisorption of HOD on a rigid Ni(100) surface using an approximate full-dimensional (9D) quantum dynamics approach, which was based on the time-dependent wave-packet calculations on a full-dimensional potential energy surface obtained through neural network fitting to density functional theory energy points. The approximate-9D probabilities were computed by averaging the seven-dimensional (7D) site-specific dissociation probabilities across six impact sites with appropriate relative weights. Our results uncover a distinctive bond-selective effect, demonstrating that the vibrational excitation of a specific bond substantially enhances the cleavage of that excited bond. The product branching ratios are substantially influenced by which bond undergoes excitation, exhibiting a clear preference for the product formed through the cleavage of the excited bond over the alternative product. [ABSTRACT FROM AUTHOR]

Grid is a free and open-source Python library for constructing numerical grids to integrate, interpolate, and differentiate functions (e.g., molecular properties), with a strong emphasis on facilitating these operations in computational chemistry and conceptual density functional theory. Although designed, maintained, and released as a stand-alone Python library, Grid was originally developed for molecular integration, interpolation, and solving the Poisson equation in the HORTON and ChemTools packages. Grid is designed to be easy to use, extend, and maintain; this is why we use Python and adopt many principles of modern software development, including comprehensive documentation, extensive testing, continuous integration/delivery protocols, and package management. We leverage popular scientific packages, such as NumPy and SciPy, to ensure high efficiency and optimized performance in grid development. This article is the official release note of the Grid library showcasing its unique functionality and scope. [ABSTRACT FROM AUTHOR]

Recently, LiGa 5 O 8 was claimed to be a p -type dopable ultrawide-bandgap oxide, based on measurements of undoped material. Here, the electronic properties of potential acceptor dopant impurities in LiGa 5 O 8 are calculated using hybrid density functional theory to evaluate their potential for causing p -type conductivity. As with the related compound LiGaO 2 , the heavy oxygen-derived valence bands lead to stable self-trapped holes in LiGa 5 O 8. Acceptor defects and dopants also bind trapped holes (or small polarons), which lead to large acceptor ionization energies. The calculations here indicate that neither native acceptor defects (such as cation vacancies or antisites) nor impurity dopants can give rise to p -type conductivity in LiGa 5 O 8. Optical transitions associated with these defects are also calculated, in order to allow for possible experimental verification of their behavior. [ABSTRACT FROM AUTHOR]

Molecular dynamics and density functional theory simulations are used to predict the lattice and electronic contributions of thermophysical properties for UN, PuN, and mixed (U,Pu)N systems. The properties predicted include the lattice parameter, linear thermal expansion, enthalpy, and specific heat capacity, as a function of temperature. The simulation predictions for high temperature specific heat capacity are compared against experimental measurements to understand the behavior, and why differences in the experimental measurements are observed. The influence of adding U vacancies, N interstitials, and Pu to UN is also examined. For this, a new PuN potential parameter set is developed and used with the Kocevski UN potential, enabling the dynamics of mixed (U,Pu)N systems to be studied. How defects impact the thermophysical properties is important for understanding fuel behavior under different reactor conditions, and these mechanistic predictions can be used to support fuel performance codes where data is scarce. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential's (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections. [ABSTRACT FROM AUTHOR]

This study presents a collaborative experimental and theoretical investigation into the structures and electronic properties of niobium-doped germanium clusters. Anion photoelectron spectra for Nb1–2Gen− (n = 3–7) clusters were acquired using 266 nm photon energies, enabling the determination of adiabatic detachment energies and vertical detachment energies. In conjunction with these experimental measurements, density functional theory (DFT) calculations were conducted to validate the experimentally obtained electron detachment energies and elucidate the geometric and electronic structures of each anionic cluster. The agreement between DFT calculations and experimental data establishes a solid foundation for assessing the structural evolution and electronic properties of niobium-doped germanium clusters. It is noted that both neutral and anionic clusters exhibit predominantly similar overall structural characteristics, with the exception of Nb2Ge6− and Nb2Ge6. Furthermore, this investigation emphasizes the exceptional chemical stability of the D3d symmetric chair-shaped structure in Nb2Ge6−, providing insights into its bonding characteristics. [ABSTRACT FROM AUTHOR]

Controlling the size distribution in the nucleation of copper particles is crucial for achieving nanocrystals with desired physical and chemical properties. However, their synthesis involves a complex system of solvents, ligands, and copper precursors with intertwining effects on the size of the nanoclusters. We combine molecular dynamics simulations and density functional theory calculations to provide insights into the nucleation mechanism in the presence of a triphenyl phosphite ligand. We identify the crucial role of the strength of the metal–phosphine interaction in inhibiting the cluster's growth. We demonstrate computationally several practical routes to fine-tune the interaction strength by modifying the side groups of the additive. Our work provides molecular insights into the complex nucleation process of protected copper nanocrystals, which can assist in controlling their size distribution and, eventually, their morphology. [ABSTRACT FROM AUTHOR]

Tetrahedrally bonded III-N and related alloys are useful for a wide range of applications from optoelectronics to dielectric electromechanics. Heterostructural AlN-based alloys offer unique properties for piezoelectrics, ferroelectrics, and other emerging applications. Atomic-scale point defects and impurities can strongly affect the functional properties of materials, and therefore, it is crucial to understand the nature of these defects and the mechanisms through which their concentrations may be controlled in AlN-based alloys. In this study, we employ density functional theory with alloy modeling and point defect calculations to investigate native point defects and unintentional impurities in Al 1 − x Gd x N alloys. Among the native defects that introduce deep midgap states, nitrogen vacancies (V N ) are predicted to be in the highest concentration, especially under N-poor growth conditions. We predict and experimentally demonstrate that V N formation can be suppressed in thin films through growth in N-rich environments. We also find that Al 1 − x Gd x N alloys are prone to high levels of unintentional O incorporation, which indirectly leads to even higher concentrations of deep defects. Growth under N-rich/reducing conditions is predicted to minimize and partially alleviate the effects of O incorporation. The results of this study provide valuable insights into the defect behavior in wurtzite nitride-based alloys, which can guide their design and optimization for various applications. [ABSTRACT FROM AUTHOR]

The orthorhombic phase of FeNbO4, a promising anode material for solid oxide fuel cells (SOFCs), exhibits good catalytic activity toward hydrogen oxidation. However, the low electronic conductivity of the material specifically in the pure structure without defects or dopants limits its practical applications as an SOFC anode. In this study, we have employed density functional theory (DFT + U) calculations to explore the bulk and electronic properties of two types of doped structures, Fe0.9375A0.0625NbO4 and FeNb0.9375B0.0625O4 (A, B = Ti, V, Cr, Mn, Co, Ni) and the oxygen-deficient structures Fe0.9375A0.0625NbO3.9375 and FeNb0.9375B0.0625O3.9375, where the dopant is positioned in the first nearest neighbor site to the oxygen vacancy. Our DFT simulations have revealed that doping in the Fe sites is energetically favorable compared to doping in the Nb site, resulting in significant volume expansion. The doping process generally requires less energy when the O-vacancy is surrounded by one Fe and two Nb ions. The simulated projected density of states of the oxygen-deficient structures indicates that doping in the Fe site, particularly with Ti and V, considerably narrows the bandgap to ∼0.5 eV, whereas doping with Co at the Nb sites generates acceptor levels close to 0 eV. Both doping schemes, therefore, enhance electron conduction during SOFC operation. [ABSTRACT FROM AUTHOR]

Identifying the oxidation structure of two-dimensional interfaces is crucial to improve surface chemistry and electronic properties. Beyond graphene with only phenyl rings, a novel carbon-nitrogen material, C3N, presents an intrinsic heterogeneous surface morphology where each phenyl ring is encircled by six nitrogen atoms, yet its atomistic oxidation structure remains unclear. Here, combining a series of density functional theory calculations and ab initio molecular dynamics simulations, we demonstrate that thermodynamically favorable oxidation loci are confined to the phenyl ring, and kinetic transformations of oxidation structures are feasible along the phenyl ring, whereas those toward nitrogen atoms are proven to be extremely difficult. These results are attributed to the lower barrier of oxygen atom migration along the phenyl ring, while the significantly high barriers toward nitrogen atoms are due to the heterogeneous potential energy surface for oxygen–C3N interaction. This work highlights the significance of surface morphology on the characteristics of oxidation structure, offering insights into tunable electronic properties via confined interfacial oxidation. [ABSTRACT FROM AUTHOR]

The photochromic behavior of the fulgide molecule relies on ring-closure and ring-opening processes involving conical intersections during excited state transformation between isomers. The precise location and topography of these conical intersections significantly shape the decay process and fluorescence phenomena inherent to the molecule. This work combines electronic structure theory calculations using the density functional theory and wavefunction methods, as well as surface hopping simulation to analyze the photochemical behavior of an experimentally synthesized fulgide molecule, (E)-p-methylacetophenylisopropylidenesuccinic anhydride (1E). Our study reveals the conical intersection between the first excited state (S1) and the ground electronic state (S0), which emerges beyond the S1 minimum of 1E to the ring-closing side. The distinctive topography of this conical intersection appears to be sloped. These findings suggest a reduced quantum yield for the formation of the closed isomer, indicating a higher likelihood of reformation of the open isomer(s). The surface hopping simulation further supports this observation, revealing a mere ∼8% quantum yield for the formation of the closed isomer. In addition, the photoisomerization of the fulgide molecule initiates a cascade of conduction switching and holds great potential for applications in molecular electronics. Delving into the realm of molecular electronics, we have further examined the electron transport properties, disclosing the higher conductivity of the closed isomer. [ABSTRACT FROM AUTHOR]

The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C–O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds. [ABSTRACT FROM AUTHOR]

In this work, the ultrafast intramolecular rotation behavior of 1,1,2,3,4,5-hexaphenylsilole has been investigated in several solutions with different viscosities using femtosecond transient absorption spectroscopy combined with density functional theory and time-dependent density functional theory calculations. It is demonstrated that the nonradiative process, which competes with radiative decay, involves two main stages, namely the restricted intramolecular rotation and internal conversion processes. The intramolecular rotation depends on viscosity and presents a significant restriction. The restricted rotational rate is determined to be dozens of picoseconds. The following nonradiative process is strongly dominated by intramolecular rotation. The nonradiative decay rate will decrease with the increase in viscosity, leading to a rise in the radiative probability and photoluminous yield. These results have borne out the mechanism of ultrafast restricted intramolecular rotation of aggregation induced emission and provided a detailed photophysical picture of nonradiative processes. [ABSTRACT FROM AUTHOR]

Warm dense matter is a highly energetic phase characterized by strong correlations, thermal effects, and quantum mechanical electrons. Thermal density functional theory is commonly used in simulations of this challenging phase, driving the development of temperature-dependent approximations to the exchange–correlation free energy. Approaches using the adiabatic connection formula are well known at zero temperature and have been recently leveraged at non-zero temperatures as well. In this work, a generalized thermal adiabatic connection (GTAC) formula is proposed, introducing a fictitious temperature parameter. This allows extraction of the exchange–correlation entropy SXC using simulated interaction strength scaling. This procedure uses a Hellmann–Feynman approach to express the exchange–correlation entropy in terms of a temperature- and interaction strength-dependent exchange–correlation potential energy. In addition, analysis of SXC as a function of interaction strength suggests new forms for approximations, and GTAC itself offers a new framework for exploring both the exact and approximate interplay of temperature, density, and interaction strength across a wide range of conditions. [ABSTRACT FROM AUTHOR]

Molecular crystals are difficult to model with accurate first-principles methods due to large unit cells. On the other hand, accurate modeling is required as polymorphs often differ by only 1 kJ/mol. Machine learning interatomic potentials promise to provide accuracy of the baseline first-principles methods with a cost lower by orders of magnitude. Using the existing databases of the density functional theory calculations for molecular crystals and molecules, we train global machine learning interatomic potentials, usable for any molecular crystal. We test the performance of the potentials on experimental benchmarks and show that they perform better than classical force fields and, in some cases, are comparable to the density functional theory calculations. [ABSTRACT FROM AUTHOR]

While computational screening with density functional theory (DFT) is frequently employed for the screening of metal–organic frameworks (MOFs) for gas separation and storage, commonly applied generalized gradient approximations (GGAs) exhibit self-interaction errors, which hinder the predictions of adsorption energies. We investigate the Hubbard U parameter to augment DFT calculations for full periodic MOFs, targeting a more precise modeling of gas molecule–MOF interactions, specifically for N2, CO2, and O2. We introduce a calibration scheme for the U parameter, which is tailored for each MOF, by leveraging higher-level calculations on the secondary building unit (SBU) of the MOF. When applied to the full periodic MOF, the U parameter calibrated against hybrid HSE06 calculations of SBUs successfully reproduces hybrid-quality calculations of the adsorption energy of the periodic MOF. The mean absolute deviation of adsorption energies reduces from 0.13 eV for a standard GGA treatment to 0.06 eV with the calibrated U, demonstrating the utility of the calibration procedure when applied to the full MOF structure. Furthermore, attempting to use coupled cluster singles and doubles with perturbative triples calculations of isolated SBUs for this calibration procedure shows varying degrees of success in predicting the experimental heat of adsorption. It improves accuracy for N2 adsorption for cases of overbinding, whereas its impact on CO2 is minimal, and ambiguities in spin state assignment hinder consistent improvements of O2 adsorption. Our findings emphasize the limitations of cluster models and advocate the use of full periodic MOF systems with a calibrated U parameter, providing a more comprehensive understanding of gas adsorption in MOFs. [ABSTRACT FROM AUTHOR]

Metal–Organic Polymers (MOPs) have attracted growing attention for lithium-ion battery (LIB) applications due to their merits in orderly ionic transportation and robust structure stability in electrochemical reactions. However, they suffer from poor electronic conductivity. In this work, we apply first-principles density functional theory to explore the potential of three one-dimensional (1D) electrically conductive C6H2S4TM (TM = Fe, Co, and Ni) MOPs with the π–d conjugated coordination as anode materials for Li+ ions storage. Our theoretical results reveal that these 1D MOPs possess a superior theoretical capacity of over 748 mA h g−1. In particular, the 1D C6H2S4Ni MOP shows an exceptional theoretical specific capacity of 1110 mA h g−1 based on the three-electron transferring reaction, which significantly outperforms the traditional graphite-based anode material in LIBs. Moreover, the resonant charge transfer between Ni metal and ligand within the 1D C6H2S4Ni MOP reduces the diffusion energy barrier of the Li atoms when they migrate on the surface of the MOP. The ultrahigh theoretical specific capacity of the C6H2S4Ni MOP predicts that it can be a promising anode material for LIBs. [ABSTRACT FROM AUTHOR]

Rare-earth doped materials are of immense interest for their potential applications in linear and nonlinear photonics. There is also intense interest in sub-nanometer gold clusters due to their enhanced stability and unique optical, magnetic, and catalytic properties. To leverage their emergent properties, here we report a systematic study of the geometries, stability, electronic, magnetic, and linear and nonlinear optical properties of Au5RE (RE = Sc, Y, La–Lu) clusters using density-functional theory. Several low-energy isomers consisting of planar or non-planar configurations are identified. For most doped clusters, the non-planar configuration is energetically favored. In the case of La-, Pm-, Gd-, and Ho-doped clusters, a competition between planar and non-planar isomers is predicted. A distinct preference for the planar configuration is predicted for Au5Eu, Au5Sm, Au5Tb, Au5Tm, and Au5Yb. The distinction between the planar and non-planar configurations is highlighted by the calculated highest frequencies, with the stretching mode of the non-planar configuration predicted to be stiffer than the planar configuration. The bonding analysis reveals the dominance of the RE-d orbitals in the formation of frontier molecular orbitals, which, in turn, facilitates retaining the magnetic characteristics governed by RE-f orbitals, preventing spin-quenching of rare earths in the doped clusters. In addition, the doped clusters exhibit small energy gaps between frontier orbitals, large dipole moments, and enhanced hyperpolarizability compared to the host cluster. [ABSTRACT FROM AUTHOR]

In the interstellar medium, diols and other prebiotic molecules adsorb onto icy mantles surrounding dust grains. Water in the ice may affect the reactivity and photoionization of these diols. Ethylene glycol (EG), 1,2-propylene glycol, and 1,3-propylene glycol clusters with water clusters were used as a proxy to study these interactions. The diol–water clusters were generated in a continuous supersonic molecular beam, photoionized by synchrotron-based vacuum ultraviolet light from the Advanced Light Source, and subsequently detected by reflectron time-of-flight mass spectrometry. The appearance energies for the detected clusters were determined from the mass spectra, collected at increasing photon energy. Clusters of both diol fragments and unfragmented diols with water were detected. The lowest energy geometry optimized conformers for the observed EG–water clusters and EG fragment–water clusters have been visualized using density functional theory (DFT), providing insight into hydrogen bonding networks and how these affect fragmentation and appearance energy. As the number of water molecules clustered around EG fragments (m/z 31 and 32) increased, the appearance energy for the cluster decreased, indicating a stabilization by water. This trend was supported by DFT calculations. Fragment clusters from 1,2-propylene glycol exhibited a similar trend, but with a smaller energy decrease, and no trend was observed from 1,3-propylene glycol. We discuss and suggest that the reactivity and photoionization of diols in the presence of water depend on the size of the diol, the location of the hydroxyl group, and the number of waters clustered around the diol. [ABSTRACT FROM AUTHOR]

A hybrid quantum mechanics/molecular mechanics setup was used to model electronically excited pentacene in the crystal phase. Particularly interesting in the context of singlet fission (SF) is the energetic location of the antiferromagnetically coupled multiexcitonic singlet state, 1(TT), and the ferromagnetically coupled analog in relation to the optically bright singlet state. To provide photophysical properties of the accessible spin manifold, combined density functional theory and multi-reference configuration interaction calculations were performed on pentacene dimers and a trimer, electrostatically embedded in the crystal. The likelihood of a quintet intermediate in the SF process was estimated by computing singlet–quintet electron spin–spin couplings employing the Breit–Pauli Hamiltonian. The performance of the applied methods was assessed on the pentacene monomer. The character of the optically bright state and the energetic location of the 1(TT) state depend strongly on the relative orientation of the pentacene units. In the V-shaped dimers and in the trimer, the optically bright state is dominated by local and charge transfer (CT) excitations, with admixtures of doubly excited configurations. The CT excitations gain weight upon geometry relaxation, thus supporting a CT-mediated SF mechanism as the primary step of the SF process. For the slip-stacked dimer, the energetic order of the bright and the 1(TT) states swaps upon geometry relaxation, indicating strong nonadiabatic coupling close to the Franck–Condon region—a prerequisite for a coherent SF process. The multiexcitonic singlet, triplet, and quintet states are energetically too far apart and their spin–spin couplings are too small to bring about a noteworthy multiplicity mixing. [ABSTRACT FROM AUTHOR]

Refractory high-entropy alloys are under consideration for applications where materials are subjected to high temperatures and levels of radiation, such as in the fusion power sector. However, at present, their scope is limited because they are highly brittle at room temperature. One suggested route to mitigate this issue is by alloying with Ti. In this theoretical study, using a computationally efficient linear-response theory based on density functional theory calculations of the electronic structure of the disordered alloys, we study the nature of atomic short-range order in these multi-component materials, as well as assessing their overall phase stability. Our analysis enables direct inference of phase transitions in addition to the extraction of an atomistic, pairwise model of the internal energy of an alloy suitable for study via, e.g., Monte Carlo simulations. Once Ti is added into either the NbMoTaW or VNbMoTaW system, we find that there is competition between chemical phase ordering and segregation. These results shed light on observed chemical inhomogeneity in experimental samples, as well as providing fundamental insight into the physics of these complex systems. [ABSTRACT FROM AUTHOR]

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal–organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C–H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production. [ABSTRACT FROM AUTHOR]

Tert-butyl functional groups can modulate the self-assembly behavior of organic molecules on surfaces. However, the precise construction of supramolecular architectures through their controlled thermal removal remains a challenge. Herein, we precisely controlled the removal amount of tert-butyl groups in tetraazaperopyrene derivatives by stepwise annealing on Ag(111). The evolution of 4tBu-TAPP supramolecular self-assembly from the grid-like structure composed of 3tBu-TAPP through the honeycomb network formed by 2tBu-TAPP to the one-dimensional chain co-assembled by tBu-TAPP and TAPP was successfully realized. This series of supramolecular nanostructures were directly visualized by high resolution scanning tunneling microscopy. Tip manipulation and density functional theory calculations show that the formation of honeycomb network structure can be attributed to the van der Waals interactions, N–Ag–N coordination bonds, and weak C–H⋯N hydrogen bonds. Further addition of two tert-butyl groups (6tBu-TAPP) leads to a completely different assembly evolution, due to the fact that the additional tert-butyl groups affect the molecular adsorption behavior and ultimately induce desorption. This work can possibly be exploited in constructing stable and long-range ordered nanostructures in surface-assisted systems, which can also promote the development of nanostructures in functional molecular devices. [ABSTRACT FROM AUTHOR]