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Pentacene is an important model organic semiconductor in both the singlet exciton fission (SF) and organic electronics communities. We have investigated the effect of changing crystal structure on the SF process, generating multiple triplet excitons from an initial singlet exciton, and subsequent triplet recombination. Unlike for similar organic semiconductors that have strong SF sensitive to polymorphism, we find almost no quantitative difference between the kinetics of triplet pair (TT) formation in the two dominant polymorphs of pentacene. Both pairwise dimer coupling and momentum-space crystal models predict much faster TT formation from the bright singlet excited state of the Bulk vs ThinFilm polymorph, contrasting with the experiment. GW and Bethe–Salpeter equation calculations, including exciton–phonon coupling, reveal that ultrafast phonon-driven transitions in the ThinFilm polymorph compensate the intrinsically slower purely Coulomb-mediated TT formation channel, rationalizing the similarity in observed rates. Taking into account the influence of subtle structural distinctions on both the direct and phonon-mediated SF pathways reveals a predictive capability to these methods, expected to be applicable to a wide variety of molecular crystals. [ABSTRACT FROM AUTHOR]

It has been recently shown that 2D systems can exhibit crystalline phases with long-range translational order showcasing a striking violation of the Hohenberg–Mermin–Wagner (HMW) theorem, which is valid at equilibrium. This is made possible by athermal driving mechanisms that inject energy into the system without exciting long wavelength modes of the density field, thereby inducing hyperuniformity. However, as thermal fluctuations are superimposed on the non-equilibrium driving, long-range translational order is inevitably lost. Here, we discuss the possibility of exploiting non-equilibrium effects to suppress arbitrarily large density fluctuations even when a global thermal bath is coupled to the system. We introduce a model of a harmonic crystal driven both by a global thermal bath and by a momentum conserving noise, where the typical observables related to density fluctuations and long-range translational order can be analytically derived and put in relation. This model allows us to rationalize the violation of the HMW theorem observed in previous studies through the prediction of large-wavelength phonons, which thermalize at a vanishing effective temperature when the global bath is switched off. The conceptual framework introduced through this theory is then applied to numerical simulations of a hard-disk solid in contact with a thermal bath and driven out-of-equilibrium by active collisions. Our numerical analysis demonstrates how varying driving and dissipative parameters can lead to an arbitrary enhancement of the quasi-long-range order in the system regardless of the applied global noise amplitude. Finally, we outline a possible experimental procedure to apply our results to a realistic granular system. [ABSTRACT FROM AUTHOR]

Crystal surfaces play a pivotal role in governing various significant processes, such as adsorption, nucleation, wetting, friction, and wear. A fundamental property that influences these processes is the surface free energy, γ. We have directly calculated γ(T) for low-index faces of Lennard-Jones (LJ), germanium, and silicon crystals along their sublimation lines using the computational cleavage technique. Our calculations agree well with experimental values for Si(111) and Ge(111), highlighting the accuracy of the method and models used. For LJ crystals, we identified a premelting onset at Tpm = 0.75Tm, marked by a sharp increase in atom mobility within the second outermost surface layer. Notably, Tpm closely aligned with the endpoint of the LJ melting line at negative pressures, Tend = 0.76Tm. We hypothesize that the emergence and coexistence of a liquid film atop the LJ crystal at Tpm < T < Tm correspond to the metastable melting line under negative pressures experienced by stretched crystal surfaces. Furthermore, our study of thin LJ crystal slabs reveals that premelting-induced failure leads to recrystallization below the homogeneous freezing limit, offering a promising avenue to explore crystal nucleation and growth at extremely deep supercoolings. Finally, no evidence of premelting was detected in the model crystals of Ge and Si, which is consistent with the experimental observations. Overall, our findings offer valuable insights into crystal surface phenomena at the atomic scale. [ABSTRACT FROM AUTHOR]

We have measured diffuse scattering in a single crystal of Cd0.9Zn0.1Te using a state-of-the-art laboratory diffractometer. A large-box atomistic simulation of a model crystal is used in conjunction with Monte Carlo modeling and the Kirkwood potential. A combination of structural relaxation in the presence of the dopant and thermal motion results in good qualitative agreement between the computed diffraction patterns of the model crystal and the measured x-ray patterns. This is shown to be rather distinct from the diffuse scattering arising from purely structural relaxations or thermal motion only. The atoms are shown to displace predominantly in ⟨1,1,1⟩ and ⟨1,0,0⟩ type directions. Our approach to Monte Carlo modeling can easily be extended to more complex defect structures to incorporate, e.g., chemical ordering on the Cd/Zn sublattice, more than one species of dopant or vacancies. [ABSTRACT FROM AUTHOR]

High-fidelity constitutive models are critical for accurate meso-scale continuum modeling and prediction of shock initiation of crystalline energetic materials (EMs). While empirically calibrated or atomistic-guided anisotropic elastoplastic models of EM such as cyclotetramethylene-tetranitramine (HMX) and cyclotrimethylene-trinitramine (RDX) capture important micromechanical phenomena (such as dislocation evolution, slip-resistance, and anisotropic elasticity), the computational cost of using anisotropic single-crystal plasticity models can become prohibitive for meso-scale computations of void-collapse and hotspot formation in microstructures. Thermo-mechanically representative, isotropic, pressure, temperature, and rate-dependent material constitutive models are practical alternatives for meso-scale simulations of the shock response of microstructures. To this end, this work constructs physically consistent isotropic plasticity from anisotropic single-crystal plasticity models for HMX and RDX. State-of-the-art crystal plasticity models for HMX and RDX are used to compute the stress states in single crystals oriented in three different directions relative to shocks generated by impact at velocities ranging from 100 to 1000 m/s. Post-shock von Mises stress fields for the three orientations are then used to calibrate the strain-rate hardening coefficient and the reference strain rate for a rate-dependent Johnson–Cook (JC) yield surface model. We compare the pressures and the post-shock von Mises stresses between the JC and the anisotropic models to show that the isotropic computations closely approximate the averaged deformation response of the three different crystal orientations. We then model the interaction of a shock generated by a 500 m/s impact with a 0.5 μm void and show that the pressures and the deviatoric stresses obtained using the isotropic model closely match those computed from anisotropic models for both HMX and RDX. The resulting isotropic J2 plastic flow model for HMX and RDX can be employed to perform meso-scale simulations for energy localization due to shear bands and void collapse in the two materials. [ABSTRACT FROM AUTHOR]

The thermal hysteresis exhibited in plastic crystal compounds greatly reduces their cyclic efficiency, limiting their potential for replacing current environmentally harmful refrigerants. A mechanistic understanding of the origins of this hysteresis has yet to be established. Here, we systematically investigate the transformation kinetics of the model plastic crystal, neopentyl glycol (NPG), through microscopic and calorimetric techniques. We reveal an asymmetry between the forward (heating) and reverse (cooling) transitions. We also demonstrate that the forward transformation is rate-limited by the rate of growth of rotationally disordered domains. In contrast, the reverse transformation is rate-limited by the nucleation of the ordered crystal domain, demonstrated by the sharp exothermic peaks in calorimetry and rapid self-nucleation phenomena observed optically. This nucleation limitation is largely responsible for the large thermal hysteresis in NPG, which we observe to be as large as 16.7 °C for an approximately 10 mg sample cooled at 0.5 °C min−1. These findings demonstrate the underlying origin of the thermal hysteresis and introduce a direction to mitigate hysteresis in plastic crystal transformations. [ABSTRACT FROM AUTHOR]

The magnetocrystalline anisotropy energy of atomically ordered L10 FeNi (the meteoritic mineral tetrataenite) is studied within a first-principles electronic structure framework. Two compositions are examined: equiatomic Fe 0.5 Ni 0.5 and an Fe-rich composition, Fe 0.56 Ni 0.44 . It is confirmed that, for the single crystals modeled in this work, the leading-order anisotropy coefficient K 1 dominates the higher-order coefficients K 2 and K 3. To enable comparison with experiment, the effects of both imperfect atomic long-range order and finite temperature are included. While our computational results initially appear to undershoot the measured experimental values for this system, careful scrutiny of the original analysis due to Néel et al. [J. Appl. Phys. 35, 873 (1964)] suggests that our computed value of K 1 is, in fact, consistent with experimental values, and that the noted discrepancy has its origins in the nanoscale polycrystalline, multivariant nature of experimental samples, that yields much larger values of K 2 and K 3 than expected a priori. These results provide fresh insight into the existing discrepancies in the literature regarding the value of tetrataenite's uniaxial magnetocrystalline anisotropy in both natural and synthetic samples. [ABSTRACT FROM AUTHOR]

It is of substantial scientific significance and practical value to reveal and understand the multiscale mechanical properties and intrinsic mechanisms of medium-entropy alloys (MEAs) under high strain rates and pressures. In this study, the mechanical responses and deformation mechanisms of an equiatomic CoCrNi MEA are investigated utilizing magnetically driven ramp wave compression (RWC) with a strain rate of 105 s−1. The CoCrNi MEA demonstrates excellent dynamic mechanical responses and yield strength under RWC compared with other advanced materials. Multiscale characterizations reveal that grain refinement and abundant micromechanisms, including dislocation slip, stacking faults, nanotwin network, and Lomer–Cottrell locks, collectively contribute to its excellent performance during RWC. Furthermore, dense deformation twins and shear bands intersect, forming a weave-like microstructure that can disperse deformation and enhance plasticity. On the basis of these observations, we develop a modified crystal plasticity model with coupled dislocation and twinning mechanisms, providing a relatively accurate quantitative description of the multiscale behavior under RWC. The results of simulations indicate that the activation of multilevel microstructures in CoCrNi MEA is primarily attributable to stress inhomogeneities and localized strain during RWC. Our research offers valuable insights into the dynamic mechanical responses of CoCrNi MEA, positioning it as a promising material for use under extreme dynamic conditions. [ABSTRACT FROM AUTHOR]

In this paper, we announce the public release of a massively parallel, graphics processing unit (GPU)-accelerated software, which is the first to combine both coarse-grained particle simulations and field-theoretic simulations in one simulation package. MATILDA.FT (Mesoscale, Accelerated, Theoretically Informed, Langevin, Dissipative particle dynamics, and Field Theory) was designed from the ground-up to run on CUDA-enabled GPUs with Thrust library acceleration, enabling it to harness the possibility of massive parallelism to efficiently simulate systems on a mesoscopic scale. It has been used to model a variety of systems, from polymer solutions and nanoparticle-polymer interfaces to coarse-grained peptide models and liquid crystals. MATILDA.FT is written in CUDA/C++ and is object oriented, making its source-code easy to understand and extend. Here, we present an overview of the currently available features, and the logic of parallel algorithms and methods. We provide the necessary theoretical background and present examples of systems simulated using MATILDA.FT as the simulation engine. The source code, along with the documentation, additional tools, and examples, can be found on the GitHub MATILDA.FT repository. [ABSTRACT FROM AUTHOR]

Understanding the dispersive properties of photonic crystals is a fundamental and well-studied problem. However, the introduction of singular permittivities and damping complicates the otherwise straightforward theory. In this paper, we study photonic crystals with a Drude–Lorentz model for the permittivity, motivated by halide perovskites. We demonstrate how the introduction of singularities and damping affects the spectral band structure and show how to interpret the notion of a "band gap" in this setting. We study a one-dimensional model for which we present explicit solutions. [ABSTRACT FROM AUTHOR]

The stress-induced martensitic transformations and superelasticity behavior in the NiTi alloy with a single crystal model and a twist grain boundary bicrystal model at different temperatures are studied using molecular dynamics simulations. An atomic tracing method is proposed to identify specific numbers of B19′ martensite variants. Under uniaxial compressive loading, the stress-induced martensitic transformation takes place accompanied by the formation of <011>M type II twins, and the deformation process can be divided into three distinct stages based on microstructure evolution and average atomic total energy. It is found that the twist grain boundary induces an increase in the martensite start temperature, which is consistent with the experimental results. There is no residual B19′ martensite at the end of the unloading process, and the irrecoverable strain mainly results from plastic deformation at the grain boundary through the analysis of atomic local shear strains and has hardly changed with increasing deformation temperature. Remarkably, the grain boundary brings about the acceleration of martensite nucleation and an earlier occurrence of stress plateau. Further simulation results manifest that the presence of the twist grain boundary leads to weakened temperature dependence of martensitic transformation stress and a reduction in the hysteresis loop area. [ABSTRACT FROM AUTHOR]

Until quite recently, in almost all papers on crystal nucleation in glass-forming substances, it was assumed that nucleation proceeds in a completely relaxed supercooled liquid and, hence, at constant values of the critical parameters determining the nucleation rate for any given set of temperature, pressure, and composition. Here, we analyze the validity of this hypothesis for a model system by studying nucleation in a lithium silicate glass treated for very long times (up to 250 days) in deeply supercooled states, reaching 60 K below the laboratory glass transition temperature, Tg. At all temperatures in the considered range, T < Tg, we observed an enormous difference between the experimental number of nucleated crystals, N(t), and its theoretically expected value computed by assuming the metastable state of the relaxing glass has been reached. Analyzing the origin of this discrepancy, we confirmed that the key parameters determining the nucleation rates change with time as a result of the glass relaxation process. Finally, we demonstrate that, for temperatures below 683 K, this particular glass almost fully crystallizes prior to reaching the ultimate steady-state nucleation regime (e.g., at 663 K, it would take 176 years for the glass to reach 99% crystallization, while 2600 years would be needed for complete relaxation). This comprehensive study proves that structural relaxation strongly affects crystal nucleation in deeply supercooled states at temperatures well below Tg; hence, this phenomenon has to be accounted for in any crystal nucleation model. [ABSTRACT FROM AUTHOR]

Until quite recently, in almost all papers on crystal nucleation in glass-forming substances, it was assumed that nucleation proceeds in a completely relaxed supercooled liquid and, hence, at constant values of the critical parameters determining the nucleation rate for any given set of temperature, pressure, and composition. Here, we analyze the validity of this hypothesis for a model system by studying nucleation in a lithium silicate glass treated for very long times (up to 250 days) in deeply supercooled states, reaching 60 K below the laboratory glass transition temperature, Tg. At all temperatures in the considered range, T < Tg, we observed an enormous difference between the experimental number of nucleated crystals, N(t), and its theoretically expected value computed by assuming the metastable state of the relaxing glass has been reached. Analyzing the origin of this discrepancy, we confirmed that the key parameters determining the nucleation rates change with time as a result of the glass relaxation process. Finally, we demonstrate that, for temperatures below 683 K, this particular glass almost fully crystallizes prior to reaching the ultimate steady-state nucleation regime (e.g., at 663 K, it would take 176 years for the glass to reach 99% crystallization, while 2600 years would be needed for complete relaxation). This comprehensive study proves that structural relaxation strongly affects crystal nucleation in deeply supercooled states at temperatures well below Tg; hence, this phenomenon has to be accounted for in any crystal nucleation model. [ABSTRACT FROM AUTHOR]

Herein, we present a new method to efficiently calculate electronically excited states in large molecular assemblies, consisting of hundreds of molecules. For this purpose, we combine the long-range corrected tight-binding density functional fragment molecular orbital method (FMO-LC-DFTB) with an excitonic Hamiltonian, which is constructed in the basis of locally excited and charge-transfer configuration state functions calculated for embedded monomers and dimers and accounts explicitly for the electronic coupling between all types of excitons. We first evaluate both the accuracy and efficiency of our fragmentation approach for molecular dimers and aggregates by comparing it with the full LC-TD-DFTB method. The comparison of the calculated spectra of an anthracene cluster shows a very good agreement between our method and the LC-TD-DFTB reference. The effective computational scaling of our method has been explored for anthracene clusters and for perylene bisimide aggregates. We demonstrate the applicability of our method by the calculation of the excited state properties of pentacene crystal models consisting of up to 319 molecules. Furthermore, the participation ratio of the monomer fragments to the excited states is analyzed by the calculation of natural transition orbital participation numbers, which are verified by the hole and particle density for a chosen pentacene cluster. The use of our FMO-LC-TDDFTB method will allow for future studies of excitonic dynamics and charge transport to be performed on complex molecular systems consisting of thousands of atoms. [ABSTRACT FROM AUTHOR]

We investigate bulk thermodynamic and microscopic structural properties of amorphous solids in the framework of the phase-field crystal (PFC) model. These are metastable states with a non-uniform density distribution, having no long-range order. From extensive numerical simulations, we determine the distribution of free energy density values in varying size amorphous systems and also the point-to-set correlation length, which is the radius of the largest volume of amorphous one can take while still having the particle arrangements within the volume determined by the particle ordering at the surface of the chosen volume. We find that in the thermodynamic limit, the free energy density of the amorphous tends toward a value that has a slight dependence on the initial state from which it was formed—i.e., it has a formation history dependence. The amorphous phase is observed to form on both sides of the liquid linear-stability limit, showing that the liquid to amorphous transition is first order, with an associated finite free energy barrier when the liquid is metastable. In our simulations, this is demonstrated when the noise in the initial density distribution is used to induce nucleation events from the metastable liquid. Depending on the strength of the initial noise, we observe a variety of nucleation pathways, in agreement with previous results for the PFC model, which show that amorphous precursor mediated multi-step crystal nucleation can occur in colloidal systems. [ABSTRACT FROM AUTHOR]

Based on the model of magnonic crystals (MCs) with honeycomb structure, we propose another model of two-dimensional MCs with honeycomb–kagome structure that is a periodic magnetic composite system composed of Fe, Co, or Py ferromagnetic cylindrical scatterers arranged in the EuO matrix as the honeycomb–kagome structure. The band structures of magnons in these systems are studied numerically by using the plane-wave expansion method. The results show that the Dirac points of magnons will be generated at the Brillouin region points if the scatterers are close-packed, that is to say, the edges of cylindrical scatterers are in contact with each other. The frequency of Dirac points can be indirectly adjusted by changing the radius ratio of close-packed cylinders. In addition, in the case of a large difference in the radius between the close-packed cylindrical scatterers, there will be a magnonic flat band in the band structure, which is a phenomenon of so-called compact localized states different from the impurity state in the crystal, and it is formed by the highly interference superposition of spin waves in the honeycomb–kagome structure. The research on the generation and modulation of magnonic Dirac points and flat bands not only expands the research content of condensed matter topological physics but also provides a promising platform for the application of artificial MCs in the fabrication of spin-wave topological devices. [ABSTRACT FROM AUTHOR]

This article focuses on computational studies evaluating the influence of crystallinity, residual stresses, and out-of-plane (OOP) deterministic switching on Terfenol-D nano/microstructures. The computational models use both coupled and uncoupled Landau–Liftshitz–Gilbert equations with elastodynamics to study strain-induced magnetization reorientation. A Voronoi tessellation approach models the crystal distribution in the microstructures subjected to residual stresses with good agreement to experimental data including large changes in coercivity values, i.e., from 100 to 3000 Oe. Parametric studies show how the coercivity is manipulated with residual stresses, including a magnetoelastically induced perpendicular-magnetic-anisotropy (PMA), important for memory applications. Additional parametric studies focus on epitaxially deposited micro-disks, revealing that residual stresses can create magnetoelastically dominant easy axes along the ⟨ 110 ⟩ directions, which are energetically favorable relative to the intrinsic ⟨ 111 ⟩ magnetocrystalline easy axes. Modification of the global easy axis is used to design a strain-mediated multiferroic composite consisting of a 20 nm epitaxially deposited Terfenol-D memory bit with PMA grown on a PZT substrate. The multiferroic disk achieves OOP deterministic clocking with an applied voltage. [ABSTRACT FROM AUTHOR]

Many macromolecules of biological and technological interest are both chiral and semi-flexible. DNA and collagen are good examples. Such molecules often form chiral nematic (or cholesteric) phases, as is well-documented in collagen and chitin. This work presents a method for studying cholesteric phases in the highly successful self-consistent field theory of worm-like chains, offering a new way of studying many biologically relevant molecules. The method involves an effective Hamiltonian with a chiral term inspired by the Oseen–Frank (OF) model of liquid crystals. This method is then used to examine the formation of cholesteric phases in chiral-nematic worm-like chains as a function of polymer flexibility, as well as the optimal cholesteric pitch and distribution of polymer segment orientations. Our approach not only allows for the determination of the isotropic–cholesteric transition and segment distributions, beyond what the OF model promises, but also explicitly incorporates polymer flexibility into the study of the cholesteric phase, offering a more complete understanding of the behavior of semiflexible chiral-nematic polymers. [ABSTRACT FROM AUTHOR]

The nematic-isotropic (NI) phase transition of 4-cyano-4′-pentylbiphenyl was simulated using the generalized replica-exchange method (gREM) based on molecular dynamics simulations. The effective temperature is introduced in the gREM, allowing for the enhanced sampling of configurations in the unstable region, which is intrinsic to the first-order phase transition. The sampling performance was analyzed with different system sizes and compared with that of the temperature replica-exchange method (tREM). It was observed that gREM is capable of sampling configurations at sufficient replica-exchange acceptance ratios even around the NI transition temperature. A bimodal distribution of the order parameter at the transition region was found, which is in agreement with the mean-field theory. In contrast, tREM is ineffective around the transition temperature owing to the potential energy gap between the nematic and isotropic phases. [ABSTRACT FROM AUTHOR]

We study the interfacial thermal conductance of grain boundaries (GBs) between monolayer graphene and hexagonal boron nitride (h-BN) sheets using a combined atomistic approach. First, realistic samples containing graphene/h-BN GBs with different tilt angles are generated using the phase-field crystal model developed recently [P. Hirvonen et al., Phys. Rev. B 100, 165412 (2019)] that captures slow diffusive relaxation inaccessible to molecular dynamics (MD) simulations. Then, large-scale MD simulations using the efficient GPUMD package are performed to assess heat transport and rectification properties across the GBs. We find that lattice mismatch between the graphene and h-BN sheets plays a less important role in determining the interfacial thermal conductance as compared to the tilt angle. In addition, we find no significant thermal rectification effects for these GBs. [ABSTRACT FROM AUTHOR]

In this article, we address the application of phase field crystal (PFC) theory, a hybrid atomistic-continuum approach, for modeling nanostructure kinetics encountered in laser deposition. We first provide an overview of the PFC methodology, highlighting recent advances to incorporate phononic and heat transport mechanisms. To simulate laser heating, energy is deposited onto a number of polycrystalline, two-dimensional samples through the application of initial stochastic fluctuations. We first demonstrate the ability of the model to simulate plasticity and recrystallization events that follow laser heating in the isothermal limit. Importantly, we also show that sufficient kinetic energy can cause voiding, which serves to suppress shock propagation. We subsequently employ a newly developed thermo-density PFC theory, coined thermal field crystal (TFC), to investigate laser heating of polycrystalline samples under non-isothermal conditions. We observe that the latent heat of transition associated with ordering can lead to long lasting metastable structures and defects, with a healing rate linked to the thermal diffusion. Finally, we illustrate that the lattice temperature simulated by the TFC model is in qualitative agreement with predictions of conventional electron–phonon two-temperature models. We expect that our new TFC formalism can be useful for predicting transient structures that result from rapid laser heating and re-solidification processes. [ABSTRACT FROM AUTHOR]

Probabilistic Markov chain modeling of photonic crystal surface emitting lasers (PCSELs) is reported. This simulation links the scattering parameters of the photonic crystal (PC) and device level losses of the PCSEL. The criteria for the conversion of the numerical model and agreement with data from the literature are discussed. We then explore the effect of increasing PC coupling coefficients and boundary mirror reflectivity on the in-plane power loss from the PCSEL. The effect of spatially varying the boundary reflectivity on the near-field is also explored. [ABSTRACT FROM AUTHOR]

An anisotropic atom–atom distributed intermolecular force-field (DIFF) for rigid trinitrobenzene (TNB) is developed using distributed multipole moments, dipolar polarizabilities, and dispersion coefficients derived from the charge density of the isolated molecule. The short-range parameters of the force-field are fitted to first- and second-order symmetry-adapted perturbation theory dimer interaction energy calculations using the distributed density-overlap model to guide the parameterization of the short-range anisotropy. The second-order calculations are used for fitting the damping coefficients of the long-range dispersion and polarization and also for relaxing the isotropic short-range coefficients in the final model, DIFF-srL2(rel). We assess the accuracy of the unrelaxed model, DIFF-srL2(norel), and its equivalent without short-range anisotropy, DIFF-srL0(norel), as these models are easier to derive. The model potentials are contrasted with empirical models for the repulsion–dispersion fitted to organic crystal structures with multipoles of iterated stockholder atoms (ISAs), FIT(ISA,L4), and with Gaussian Distributed Analysis (GDMA) multipoles, FIT(GDMA,L4), commonly used in modeling organic crystals. The potentials are tested for their ability to model the solid state of TNB. The non-empirical models provide more reasonable relative lattice energies of the three polymorphs of TNB and propose more sensible hypothetical structures than the empirical force-field (FIT). The DIFF-srL2(rel) model successfully has the most stable structure as one of the many structures that match the coordination sphere of form III. The neglect of the conformational flexibility of the nitro-groups is a significant approximation. This methodology provides a step toward force-fields capable of representing all phases of a molecule in molecular dynamics simulations. [ABSTRACT FROM AUTHOR]

We establish an approach to compute linear-response functions to elucidate heat waves and non-local thermal transport. The theory is able to describe the response of a system to external heat sources that are nonuniform in space and time. The response functions are computed using equilibrium molecular-dynamics simulations of an Ar crystal modeled using the standard Lennard–Jones potential. It is shown that for low temperatures and short length scales, transport can be partially or even completely ballistic, with the response primarily limited by the group velocity of lattice waves. By contrast, at longer length scales and higher temperatures, the response functions correspond more closely to diffusive transport characteristic of Fourier's law. It is also shown how the effective thermal conductivity can be determined in a partially ballistic regime. The results demonstrate the known reduction in the effective thermal conductivity observed when system dimensions are smaller than the mean-free path for lattice waves. Finally, we show how the determination of relevant response functions can be used to model heating of a crystal without requiring additional atomic-scale simulations. Differences between computed results and predictions from Fourier's law represent wave-like, partially ballistic transport. [ABSTRACT FROM AUTHOR]

The lattice parameters of A2XY6 (A = K, Cs, Rb, and Tl; X = tetravalent cation; Y = F, Cl, Br, and I) cubic crystals play significant roles in designing materials for specific technological applications and uniquely describe the material crystal structure. Despite the importance of its lattice parameters, the experimental determination of these parameters requires special sophisticated equipment, while the first principle calculation consumes appreciable time and might need complex software packages. The existing empirical relation in the literature is characterized by large percentage deviation, and the recently proposed machine learning support vector regression method cannot be empirically implemented on new compounds. This present work fills the research gap through the development of empirical relation between the lattice parameters, electronegativity and ionic radii of the constituting ions using extreme learning machine (ELM) with the grid search (GS) hyper-parameters optimization method. The proposed model is developed through the analysis of atomic structural properties of 85 crystals that serve as representatives of the A2XY6 group. On the basis of a mean absolute percentage error, the developed GS-ELM model outperforms the existing Brik and Kityk [J. Phys. Chem. Solids 72(11), 1256–1260 (2011)] model with a percentage improvement of 58.37%, while it performs better than Alade et al. [J. Appl. Phys. 127(1), 15303 (2020)] model with the percentage enhancement of 37.90%. The outstanding performance of the proposed GS-ELM model coupled with its ease of implementation would be of great significance by enhancing the search for new materials tailored to targeted application and preventing lattice constant mismatch in thin film fabrication. [ABSTRACT FROM AUTHOR]

Electron–phonon coupling plays a central role in the transport properties and photophysics of organic crystals. Successful models describing charge- and energy-transport in these systems routinely include these effects. Most models for describing photophysics, on the other hand, only incorporate local electron–phonon coupling to intramolecular vibrational modes, while nonlocal electron–phonon coupling is neglected. One might expect nonlocal coupling to have an important effect on the photophysics of organic crystals because it gives rise to large fluctuation in the charge-transfer couplings, and charge-transfer couplings play an important role in the spectroscopy of many organic crystals. Here, we study the effects of nonlocal coupling on the absorption spectrum of crystalline pentacene and 7,8,15,16-tetraazaterrylene. To this end, we develop a new mixed quantum–classical approach for including nonlocal coupling into spectroscopic and transport models for organic crystals. Importantly, our approach does not assume that the nonlocal coupling is linear, in contrast to most modern charge-transport models. We find that the nonlocal coupling broadens the absorption spectrum non-uniformly across the absorption line shape. In pentacene, for example, our model predicts that the lower Davydov component broadens considerably more than the upper Davydov component, explaining the origin of this experimental observation for the first time. By studying a simple dimer model, we are able to attribute this selective broadening to correlations between the fluctuations of the charge-transfer couplings. Overall, our method incorporates nonlocal electron–phonon coupling into spectroscopic and transport models with computational efficiency, generalizability to a wide range of organic crystals, and without any assumption of linearity. [ABSTRACT FROM AUTHOR]

The whole optical phonon spectrum of quasiconfined (CO), propagating (PR), and interface (IF) modes in wurtzite III-nitride cylindrical core-multishell nanowires (CMSNWs) is obtained based on the dielectric continuum and Loudon's uniaxial crystal models considering the ternary mixed crystal effect. A transfer matrix method calculation shows that there are six types of CO modes and one type of PR mode in a three-layered CMSNW. For any fixed component, only permitted types of CO modes exist in allowable frequency regions, while the PR modes appear only when components are almost the same in all layers, originating from anisotropic optical phonons in bulk wurtzite nitride. The whole spectrum reveals two mode transformations: one is between PR and IF modes by adjusting components in different layers; the other is continuous among five possible modes at any fixed component with connected frequency regions. The dispersion relations and corresponding electrostatic potentials of the whole optical phonon spectrum are helpful to understand the frequency-dependent electron–phonon interaction in the future. The analysis process can be extended to arbitrary nitride cylindrical CMSNWs for the modulation of optical phonon related properties. [ABSTRACT FROM AUTHOR]

Lattice constant mismatch between materials affects the quality of thin film fabrication. For this reason, lattice constants information is vital in the design of materials for technological applications. The determination of lattice constants via experimental analysis is relatively expensive and laborious. As a result, several linear empirical models have been proposed to predict the lattice constant of crystal structures. However, the accuracies of these models are limited partly due to their failure to account for nonlinearity in the atomic parameters-lattice constant relationship. Machine learning techniques have shown excellent ability to deal with nonlinear problems in many areas of materials science; hence, they are considered suitable computation tools to study the crystal structure of materials. In this contribution, we developed a support vector regression (SVR) model to predict the lattice constant of cubic crystals of the form A2XY6 (A = K, Cs, Rb, TI; X = tetravalent cation; and Y = F, Cl, Br, I). The SVR algorithm uses the ionic radii and electronegativities data of the constituent elements of A2XY6 cubic crystals as model inputs. The robustness of the proposed model was demonstrated by comparing our result with an existing linear model based on 26 cubic crystal samples. The result revealed a total relative deviation of 1.757 and 2.704 for the SVR model and the existing linear equation, respectively. This result proves that the SVR model has a huge potential in the search for new materials for different applications. [ABSTRACT FROM AUTHOR]

We have extended the multiconfigurational Ehrenfest (MCE) approach to investigate the dynamics of a one-dimensional Holstein molecular crystal model. It has been shown that the extended MCE approach yields results in perfect agreement with benchmark calculations by the hierarchy equations of motion method. The accuracies of the MCE approach in describing the dynamical properties of the Holstein polaron over a wide range of exciton transfer integrals and exciton-phonon couplings are carefully examined by a detailed comparison with the fully variational multiple Davydov D2 ansatz. It is found that while the MCE approach and the multi-D2 ansatz produce almost exactly the same results for a small transfer integral, the results obtained by the multi-D2 ansatz start to deviate from those by the MCE approach at longer times for a large transfer integral. A large number of coherent state basis functions are required to characterize the delocalized features of the phonon wavefunction in the case of large transfer integral, which becomes computationally too demanding for the multi-D2 ansatz. The MCE approach, on the other hand, uses hundreds to thousands of trajectory guided basis functions and converges very well, thus providing an effective tool for accurate and efficient simulations of polaron dynamics. [ABSTRACT FROM AUTHOR]

Accurate analysis of pair correlations in condensed matter allows us to establish relations between structures and thermodynamic properties and, thus, is of high importance for a wide range of systems, from solids to colloidal suspensions. Recently, the interpolation method (IM) that describes satisfactorily the shape of pair correlation peaks at short and at long distances has been elaborated theoretically and using molecular dynamics simulations, but it has not been verified experimentally as yet. Here, we test the IM by particle-resolved studies with colloidal suspensions and with complex (dusty) plasmas and demonstrate that, owing to its high accuracy, the IM can be used to experimentally measure parameters that describe interaction between particles in these systems. We used three- and two-dimensional colloidal crystals and monolayer complex (dusty) plasma crystals to explore suitability of the IM in systems with soft to hard-sphere-like repulsion between particles. In addition to the systems with pairwise interactions, if many-body interactions can be mapped to the pairwise ones with some effective (e.g., density-dependent) parameters, the IM could be used to obtain these parameters. The results reliably show that the IM can be effectively used for analysis of pair correlations and interactions in a wide variety of systems and therefore is of broad interest in condensed matter, complex plasma, chemical physics, physical chemistry, materials science, and soft matter. [ABSTRACT FROM AUTHOR]

Finding the possible stopping sites for muons inside a crystalline sample is a key problem of muon spectroscopy. In a previous study, we suggested a computational approach to this problem when dealing with muonium, the pseudoatom formed by a positive muon that has captured an electron, using density functional theory software in combination with a random structure searching approach that relies on a Poisson sphere distribution. In this work, we test this methodology further by applying it to muonium in three organic molecular crystal model systems: durene, bithiophene, and tetracyanoquinodimethane. Using the same sets of random structures, we compare the performance of density functional theory software CASTEP and the much faster lower level approximation of Density Functional Tight Binding provided by DFTB+ combined with the use of the 3ob-3-1 parameter set. We show the benefits and limitations of such an approach, and we propose the use of DFTB+ as a viable alternative to more cumbersome simulations for routine site-finding in organic materials. Finally, we introduce the Muon Spectroscopy Computational Project software suite, a library of Python tools meant to make these methods standardized and easy to use. [ABSTRACT FROM AUTHOR]

An additive quantum mechanics/molecular mechanics (QM/MM) model for the theoretical investigation of molecular crystals (AC-QM/MM) is presented. At the one-body level, a single molecule is chosen as the QM region. The MM region around it consists of a finite cluster of explicit MM atoms, represented by point charges and Lennard-Jones potentials, with additional background charges to mimic periodic electrostatics. Cluster charges are QM-derived and calculated self-consistently to ensure a polarizable embedding. We have also considered the extension to many-body QM corrections, calculating the interactions of a central molecule to neighboring units in the crystal. Full gradient expressions have been derived, also including symmetry information. The scheme allows for the calculation of molecular properties as well as unconstrained optimizations of the molecular geometry and cell parameters with respect to the lattice energy. Benchmarking the approach with the X23 reference set confirms the convergence pattern of the many-body extension although a comparison to plane-wave density functional theory reveals a systematic overestimation of cohesive energies by 6–16 kJ mol−1. While the scheme primarily aims to provide an inexpensive and flexible way to model a molecule in a crystal environment, it can also be used to reach highly accurate cohesive energies by the straightforward application of wave function correlated approaches. Calculations with local coupled cluster with singles, doubles, and perturbative triples, albeit limited to numerical gradients, show an impressive agreement with experimental estimates for small molecular crystals. [ABSTRACT FROM AUTHOR]

Molecular ferroelectrics are a promising class of ferro-electrics, with environmental friendliness, flexibility and low cost. In this work, a set of characteristic molecular ferroelectrics are simulated by molecular dynamics (MD) with polarized crystal charge (PCC). From the simulated results, their ferroelectric switching mechanisms are elucidated, with their ferroelectric hysteresis loops. The PCC charge model, recently developed by our group, containing the quantum electric polarization effect, is suitable in nature for studying molecular ferroelectrics. The simulated systems include the typical molecular ionic ferroelectrics, di-isopropyl-ammonium halide (DIPAX, X=C (Cl), B (Br), and I), as well as a pair of newly validated organic molecular ferroelectrics, salicylideneaniline and (-)-camphanic acid. In total, there are five systems under investigation. Results demonstrate that the PCC MD method is efficient and reliable. It not only elucidates the ferroelectric switching mechanism of the studied molecular ferroelectrics, but also extends the application range of the PCC MD. In conclusion, PCC MD provides an efficient protocol for extensive computer simulations of molecular ferroelectrics, with reliable ferroelectric properties and associated mechanisms, and would promote further exploration of novel molecular ferroelectrics. [ABSTRACT FROM AUTHOR]

We report the design and fabrication of a vertical structure using a distributed Bragg reflector and dielectric material layer to achieve optimized optical absorption enhancement for a stack of monolayer WS2 and MoS2, namely, a tenfold increase in absorption over a 100 nm spectral range. Our research indicates that we can approach over 50% absorption by finely tuning the thickness of the spacer layer. Our theoretical model shows that the dependence of the absorption coefficient on the spacer thickness can be understood as a solution of a non-Hermitian Schrödinger equation. These results advance the development of broadband optical devices, including solar energy conversion and sensitive optical sensors, by using two-dimensional excitonic materials. [ABSTRACT FROM AUTHOR]

To facilitate the analysis of pattern formation and the related phase transitions in Bose–Einstein condensates, we present an explicit approximate mapping from the nonlocal Gross–Pitaevskii equation with cubic nonlinearity to a phase field crystal (PFC) model. This approximation is valid close to the superfluid–supersolid phase transition boundary. The simplified PFC model permits the exploration of bifurcations and phase transitions via numerical path continuation employing standard software. While revealing the detailed structure of the bifurcations present in the system, we demonstrate the existence of localized states in the PFC approximation. Finally, we discuss how higher-order nonlinearities change the structure of the bifurcation diagram representing the transitions found in the system. [ABSTRACT FROM AUTHOR]

We present a detailed theory of the effects of crystal orientation on the properties of semiconductors. Our formalism allows us to study arbitrary crystallographic orientations of various compound semiconductors within any band model and crystal symmetry. For an illustration of its applicability, we present here results (band structure and effective masses) for only a few higher symmetry substrate orientations and concentrate on bulk cubic systems for materials such as GaInPAs/GaAs, GaInPAs/InP, GaInAsSb/GaSb, and GaInAsSb/InAs. Such cases were not discussed before. [ABSTRACT FROM AUTHOR]

Given the multitude of growth habits, pronounced sensitivity to ambient conditions and wide range of scales involved, snowflake crystals are particularly challenging systems to simulate. Only a few models are able to reproduce the diversity observed regarding snowflake morphology. It is particularly difficult to perform reliable numerical simulations of snow crystals. Here, we present a modified phase-field model that describes vapor-ice phase transition through anisotropic surface tension, surface diffusion, condensation, and water molecule depletion rate. The present work focuses on the development and validation of such a coupled flow/species/phase solver in two spatial dimensions based on the lattice Boltzmann method. It is first shown that the model is able to correctly capture species and phase growth coupling. Furthermore, through a study of crystal growth subject to ventilation effects, it is shown that the model correctly captures hydrodynamics-induced asymmetrical growth. The validated solver is then used to model snowflake growth under different ambient conditions with respect to humidity and temperature in the plate-growth regime section of the Nakaya diagram. The resulting crystal habits are compared to both numerical and experimental reference data available in the literature. The overall agreement with experimental data shows that the proposed algorithm correctly captures both the crystal shape and the onset of primary and secondary branching instabilities. As a final part of the study, the effects of forced convection on snowflake growth are studied. It is shown, in agreement with observations in the literature, that under such conditions the crystal exhibits nonsymmetrical growth. The non-uniform humidity around the crystal due to forced convection can even result in the coexistence of different growth modes on different sides of the same crystal. [ABSTRACT FROM AUTHOR]

We describe an automated gas sampling and injection unit for a gas chromatograph (GC). It has specially been designed for low concentrations of products formed in catalytic in situ and operando experiments when slow reactions on single crystal models are investigated. The unit makes use of a buffer volume that is filled with gas samples from the reactor at a reduced pressure. The gas samples are then compressed by He to the injection pressure of 1000 mbar and pushed into two sample loops of the GC, without major intermixing with He. With an additional cryo trap at one of the GC column heads, the design aims at concentrating the gas samples and focusing the peaks. The performance is characterized by experiments on the Fischer–Tropsch synthesis, using H2/CO mixtures (syngas) at 200 and 950 mbar and a Co(0001) single crystal sample as model catalyst. Chromatograms recorded during the reaction display sharp, well separated peaks of saturated and unsaturated C1 to C4 hydrocarbons formed by the reaction, whereas the syngas matrix only gives moderate signals that can be well separated from the product peaks. Detection and quantification limits of 0.4 and 1.3 ppb, respectively, have been achieved and turnover numbers as low as 10−5 s−1 could be measured. The system can be combined with all known analysis techniques used in in situ and operando experiments. [ABSTRACT FROM AUTHOR]

The biintercalation of the layered GaSe semiconductor is carried out by ferroelectric and ferromagnetic guest components. Due to the separation of guest components, the GaSe nanohybrid has a spatial-scale hybridity, which is due to the alternation of nanoscale regions of one phase with meso- or microdimensions of another. The results of electrical conductivity studies by impedance spectroscopy indicate a 250-fold increase after biintercalation of the GaSe single crystal, due to delocalized current carriers. Confirmation of a significant change in the impurity energy spectrum after biintercalation was obtained by the method of thermally stimulated discharge—GaSe nanohybrid is characterized by a quasi-continuous spectrum in the entire temperature range of measurements and relaxation of the heterocharge. The GaSe nano-hybrid is characterized by a high dielectric constant while a tangent of the dielectric loss angle is less than 1 in the high- frequency region of the spectrum. That opens the prospect of its use for the manufacture of high-quality radio- frequency capacitors. Changes in the impurity energy spectrum are investigated for low temperatures in the virtual crystal model, taking into account the Fivazov dispersion law both for the conductivity band and for the two impurity bands. The appearance of an additional gap in the spectrum of impurity states is established and its shift is investigated depending on the concentration of intercalants of different nature—intercalant-acceptor type and donor. [ABSTRACT FROM AUTHOR]