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DOE OSTI2024

Controlling phase transitions in MnNiGe using thermal quenching and hydrostatic pressure

Here, the phase transitions in MnNiGe compounds were explored by manipulating the heat treatment conditions and through hydrostatic pressure application. As the quenching temperature increased, both the first-order martensitic structural transition temperatures and magnetic transition temperatures decreased relative to those in the slowly-cooled samples. When the samples were quenched from 1200 °C, the first-order martensitic structural transition temperature lowered by more than 200 K. The structural transitions also shifted to lower temperature with the application of hydrostatic pressure during measurement. Temperature-dependent x-ray diffraction results reveal that the changes of the cell parameters resulting from the structural transitions are nearly identical for all samples regardless of the extensive variation in their structural transition temperatures. In addition, neutron scattering measurements confirm the magnetic structure transition between simple and cycloidal spiral magnetic structures.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Experimental observation of electron-scale turbulence evolution across the L–H transition in the National Spherical Torus Experiment

Electron-scale turbulence (for $3$ $\lesssim$ $k⟂ρ_s$ $\lesssim$ $12$) ) was measured during the L–H transition in the National Spherical Torus Experiment (NSTX) (Ono et al 2000 Nucl. Fusion 40 557) using a coherent microwave scattering system. The measurements were carried out at a radial region adjacent to the edge transport barrier (ETB) (at smaller radius than ETB). The observed L–H transition occurred during current flattop, which facilitated the measurement of electron-scale turbulence. The measured electron-scale turbulence is observed to be quasi-stationary before the L–H transition, and an intermittent phase for electron-scale turbulence is observed after the start of the L–H transition with a gradual decrease in overall turbulence density fluctuation spectral power with intermittent large relative variations (on ~0.5–1 ms time scale) in the total spectral power. A turbulence-quiescent phase is observed following the intermittent phase, and a significant reduction in the electron-scale turbulence spectral power is only observed at lower wavenumbers, namely $k⟂ρ_s$ $\leqslant$ $9$ –10, which is also seen in different operational NSTX scenarios due to different stabilization mechanisms. A recovery phase is seen after the quiescent phase, where the electron-scale density fluctuation power starts to gradually increase. Simultaneous ion-scale turbulence measurements at larger radius than the electron-scale turbulence measurement location show similar temporal behavior in ion-scale turbulence as in the measured electron-scale turbulence. These observations demonstrate that the suppression of turbulence during the L–H transition is not just limited to the ETB region. None of the measured electron-scale turbulence and ion-scale turbulence from edge into core is found to be obviously leading in the response to the L–H transition, and the overall turbulence suppression after the start of the L–H transition at different radii seems to start at the same time and is a gradual process happening on a tens-of-ms time scale. The trend of decrease in electron-scale turbulence during the L–H transition is found to be consistent with a decrease in the maximum electron-temperature-gradient linear growth rate from linear gyrokinetic stability analysis. Interestingly, the observed intermittency in electron-scale turbulence during the intermittent phase cannot be explained by the linear analysis.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2023

Oscillating paramagnetic Meissner effect and Berezinskii-Kosterlitz-Thouless transition in underdoped Bi2Sr2CaCu2O8+δ

ABSTRACT Superconducting phase transitions in two dimensions lie beyond the description of the Ginzburg-Landau symmetry-breaking paradigm for three-dimensional superconductors. They are Berezinskii-Kosterlitz-Thouless (BKT) transitions of paired-electron condensate driven by the unbinding of topological excitations, i.e. vortices. The recently discovered monolayers of layered high-transition-temperature (${{{T}}}_{{\rm C}}$) cuprate superconductor Bi2Sr2CaCu2O8+δ (Bi2212) meant that this 2D superconductor promised to be ideal for the study of unconventional superconductivity. But inhomogeneity posed challenges for distinguishing BKT physics from charge correlations in this material. Here, we utilize the phase sensitivity of scanning superconducting quantum interference device microscopy susceptometry to image the local magnetic response of underdoped Bi2212 from the monolayer to the bulk throughout its phase transition. The monolayer segregates into domains with independent phases at elevated temperatures below ${{{T}}}_{{\rm C}}$. Within a single domain, we find that the susceptibility oscillates with flux between diamagnetism and paramagnetism in a Fraunhofer-like pattern up to ${{{T}}}_{{\rm C}}$. The finite modulation period, as well as the broadening of the peaks when approaching ${{{T}}}_{{\rm C}}$ from below, suggests well-defined vortices that are increasingly screened by the dissociation of vortex-antivortex plasma through a BKT transition. In the multilayers, the susceptibility oscillation differs in a small temperature regime below ${{{T}}}_{{\rm C}}$, consistent with a dimensional crossover led by interlayer coupling. Serving as strong evidence for BKT transition in the bulk, we observe a sharp jump in phase stiffness and paramagnetism at small fields just below ${{{T}}}_{{\rm C}}$. These results unify the superconducting phase transitions from the monolayer to the bulk underdoped Bi2212, and can be collectively referred to as the BKT transition with interlayer coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Quantum simulation of quantum phase transitions using the convex geometry of reduced density matrices

Transitions of many-particle quantum systems between distinct phases at absolute-zero temperature, known as quantum phase transitions, require an exacting treatment of particle correlations. Here in this work, we present a general quantum-computing approach to quantum phase transitions that exploits the geometric structure of reduced density matrices. While typical approaches to quantum phase transitions examine discontinuities in the order parameters, the origin of phase transitions—their order parameters and symmetry breaking—can be understood geometrically in terms of the set of two-particle reduced density matrices (2-RDMs). The convex set of 2-RDMs provides a comprehensive map of the quantum system including its distinct phases as well as the transitions connecting these phases. Because 2-RDMs can potentially be computed on quantum computers at nonexponential cost, even when the quantum system is strongly correlated, they are ideally suited for a quantum-computing approach to quantum phase transitions. We compute the convex set of 2-RDMs for a Lipkin-Meshkov-Glick spin model on IBM superconducting-qubit quantum processors. Even though computations are limited to few-particle models due to device noise, comparisons with a classically solvable 1000-particle model reveal that the finite-particle quantum solutions capture the key features of the phase transitions including the strong correlation and the symmetry breaking.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2020

Pressure tuning of structural and magnetic transitions in EuAg 4 As 2

We report temperature-dependent measurements of ambient-pressure specific heat, magnetic susceptibility, anisotropic resistivity, and thermal expansion as well as in-plane resistivity under pressure up to 20.8 kbar on single crystals of EuAg 4 As 2 . Based on thermal expansion and in-plane electrical transport measurements at ambient pressure this compound has two, first-order, structural transitions in the 80–120 K temperature range. Ambient-pressure specific heat, magnetization, and thermal expansion measurements show a cascade of up to seven transitions between 8 and 16 K associated with the ordering of the $Eu^{2+}$ moments. In-plane electrical transport is able to detect the more prominent of these transitions, at 15.5, 9.9, and 8.7 K, as well as a weak feature at 11.8 K at ambient pressure. Pressure-dependent electrical transport data show that the magnetic transitions shift to higher temperatures under pressure, as does the upper structural transition, whereas the lower structural transition is suppressed and ultimately vanishes. A jump in resistivity, associated with the upper structural transition, decreases under pressure with an extrapolated disappearance (or a change of sign) by 30–35 kbar. In the 10–15 kbar range a kink in the pressure dependency of the upper structural transition temperature as well as the high- and low-temperature in-plane resistivities suggests that a change in the electronic structure may occur in this pressure range. The results are compared with the literature data for EuAg 4 As 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Search for in-band transitions in the candidate superdeformed band in Si 28

Background: Superdeformed (SD) bands are suggested by theory around Ca 40 and in lighter alpha-conjugate nuclei such as Mg 24 , Si 28 , and S 32 . Such predictions originate from a number of theoretical models including mean-field models and antisymmetrized molecular dynamics (AMD) calculations. While SD bands have been identified in Ca 40 and its near neighbors, evidence of their existence in the lighter, midshell nuclei is circumstantial at best. Additionally, the key evidence of superdeformation would be the observation of transitions with high B ( E 2 ) transition strengths connecting states in a rotational sequence. This is challenging information to obtain since the bands lie at a high excitation energy and competition from out-of-band decay is dominant. Purpose: The purpose of the present study is to establish a new methodology to circumvent the difficulties in identifying and quantifying in-band transitions through directly populating candidate states in the SD band in Si 28 through inelastic alpha scattering, selecting such states with a spectrometer, and measuring their gamma-ray decay with a large array of high-purity germanium detectors, allowing direct access to electromagnetic transition strengths. Methods: Excited states in Si 28 were populated in the Si 28 ( α , α ' ) reaction using a 130-MeV He 4 beam from the K140 AVF cyclotron at the Research Center for Nuclear Physics. Outgoing alpha particles were analyzed using the Grand Raiden spectrometer positioned at an angle of 9 . 1 ° to favor the population of states with J ≈ 4 . Coincident gamma rays were detected with the CAGRA array of 12 HPGe clover detectors augmented by a set of four large LaBr 3 detectors. Results: Data analysis showed that it was possible to identify additional low-energy transitions in competition with high-energy decays from excited states in Si 28 in the vicinity of 10 MeV. However, while the candidate 4 + SD state at 10.944 MeV was populated, a 1148-keV transition to the candidate 2 + SD state at 9.796 MeV was not observed, and only an upper limit for its transition strength of B ( E 2 ) < 43 W.u. could be established. This contradicts AMD predictions of ≈ 200 W.u. for such a transition. Conclusion: The present study strongly rejects the hypothesis that the candidate set of states identified in Si 28 represents an SD band, which demonstrates the potential of the methodology devised here.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2024

Evolution of the Fermi Surface of 1T-VSe 2 across a Structural Phase Transition

Periodic lattice distortion, known as the charge density wave, is generally attributed to electron–phonon coupling. This correlation is expected to induce a pseudogap at the Fermi level in order to gain the required energy for stable lattice distortion. The transition metal dichalcogenide 1T-VSe 2 also undergoes such a transition at 110 K. Here, we present detailed angle-resolved photoemission spectroscopy experiments to investigate the electronic structure in 1T-VSe 2 across the structural transition. Previously reported warping of the electronic structure and the energy shift of a secondary peak near the Fermi level as the origin of the charge density wave phase are shown to be temperature independent and hence cannot be attributed to the structural transition. Our work reveals new states that were not resolved in previous studies. Earlier results can be explained by the different dispersion natures of these states and temperature-induced broadening. Only the overall size of the Fermi surface is found to change across the structural transition. These observations, quite different from the charge density wave scenario commonly considered for 1T-VSe 2 and other transition metal dichalcogenides, bring fresh perspectives toward correctly describing structural transitions. Therefore, these new results can be applied to material families in which the origin of the structural transition has not been resolved.

36 MATERIALS SCIENCE↗

DOE OSTI2020

A White Dwarf with Transiting Circumstellar Material Far outside the Roche Limit

We report the discovery of a white dwarf exhibiting deep, irregularly shaped transits, indicative of circumstellar planetary debris. Using Zwicky Transient Facility DR2 photometry of ZTF J013906.17+524536.89 and follow-up observations from the Las Cumbres Observatory, we identify multiple transit events that recur every ≈107.2 days, much longer than the 4.5–4.9 hr orbital periods observed in WD 1145+017, the only other white dwarf known with transiting planetary debris. The transits vary in both depth and duration, lasting 15–25 days and reaching 20%–45% dips in flux. Optical spectra reveal strong Balmer lines, identifying the white dwarf as a DA with ${T}_{\mathrm{eff}}=10,530\pm 140\,{\rm{K}}$ and $\mathrm{log}(g)=7.86\pm 0.06$. A Ca ii K absorption feature is present in all spectra both in and out of transit. Spectra obtained during one night at roughly 15% transit depth show increased Ca ii K absorption with a model atmospheric fit suggesting [Ca/H] = –4.6 ± 0.3, whereas spectra taken on three nights out of transit have [Ca/H] of –5.5, –5.3, and –4.9 with similar uncertainties. While the Ca ii K line strength varies by only 2σ, we consider a predominantly interstellar origin for Ca absorption unlikely. Here, we suggest a larger column density of circumstellar metallic gas along the line of site or increased accretion of material onto the white dwarf's surface are responsible for the Ca absorption, but further spectroscopic studies are required. In addition, high-speed time series photometry out of transit reveals variability with periods of 900 and 1030 s, consistent with ZZ Ceti pulsations.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS2019

Laminar-Turbulent Transition Upstream of the Entropy-Layer Swallowing Location in Hypersonic Boundary Layers

Numerical and experimental studies have demonstrated that modal growth of planar Mack modes is responsible for laminar-turbulent transition on sharp cones at hypersonic speeds. However, the physical mechanisms that lead to transition onset upstream of the entropy-layer swallowing location over sufficiently blunt geometries are not well understood as yet. Modal amplification is too weak or nonexistent to initiate transition at moderate-to-large bluntness values. Nonmodal analysis shows that, with increasing nose bluntness, both planar and oblique traveling disturbances that peak within the entropy layer experience appreciable energy amplification. However, because of the relatively weak signature of the nonmodal traveling disturbances within the boundary-layer region, the route to transition onset subsequent to the nonmodal growth remains unclear. Thus, nonlinear parabolized stability equations (NPSE) and direct numerical simulations (DNS) have been used to investigate the potential transition mechanisms over a 7-degree blunt cone that was tested in the AFRL Mach-6 high-Reynoldsnumber facility. Computations are performed to separately follow the nonlinear development of two classes of inflow disturbances, namely, a pair of oblique traveling waves with equal but opposite angles with respect to the mean flow direction and a planar traveling wave. Results in both cases show an excellent agreement between the NPSE and DNS predictions, establishing that the NPSE is an accurate and efficient technique for predicting the nonlinear development for these particular nonmodal traveling disturbances. Computations reveal that the oblique mode interactions lead to the generation of stationary streaks inside the boundary layer that, in turn, facilitate the growth of a subharmonic sinuous disturbance. For relatively modest amplitudes of the inflow disturbance, the oblique-mode breakdown can lead to transition at the measured location of transition onset during the experiment. On the other hand, the nonlinear development of a planar traveling wave leads to the formation of inclined structures just above the boundary-layer edge and these structures are strongly reminiscent of the transitional events observed during blunt cone experiments by using schlieren flow visualizations.

Entropy↗

NASA NTRS2019

Boundary Layer Stability and Laminar-Turbulent Transition Analysis with Thermochemical Nonequilibrium Applied to Martian Atmospheric Entry

As Martian atmospheric entry vehicles increase in size to accommodate larger payloads, transitional ow may need to be taken into account in the design of the heat shield in order to reduce heat shield mass. The mass of the Thermal Protection System (TPS) comprises a significant portion of the vehicle mass, and a reduction of this mass would result in fuel savings. The current techniques used to design entry shields generally assume fully turbulent flow when the vehicle is large enough to expect transitional flow, and while this worst-case scenario provides a greater factor of safety it may also result in overdesigned TPS and unnecessarily high vehicle mass. Greater accuracy in the prediction of transition would also reduce uncertainty in the thermal and aerodynamic loads. Stability analysis, using e(sup⁡ N) -based methods including Linear Stability Theory (LST) and the Parabolized Stability Equations (PSE), offers a physics-based method of transition prediction that has been thoroughly studied and applied in perfect gas flows, and to a more limited extent in reacting and nonequilibrium flows. These methods predict the amplification of a known disturbance frequency and allow identification of the most unstable frequency. Transition is predicted to occur at a critical amplification or N Factor, frequently determined through experiment and empirical correlations. The LAngley Stability and TRansition Analysis Code (LASTRAC), with modifications for thermochemically reacting flows and arbitrary gas mixtures, will be presented with LST results on a simulation of a high enthalpy CO2 gas wind tunnel test relevant to Martian atmospheric entry. The results indicate transition caused by modified Tollmien-Schlichting waves on the leeward side, which are predicted to be more stable and cause transition slightly downstream when thermochemical nonequilibrium is included in the stability analysis for the same mean flow solution.

Transition↗

NASA NTRS2021

Modeling Laminar-to-Turbulent Transition in the Panel Test Facility Arcjet

A computational fluid dynamics (CFD) laminar-to-turbulence transition model was developed for the NASA Ames Research Center’s 20 MW Panel Test Facility (PTF). Surface pressure, heat flux to a water-cooled plate, and surface temperature on a tile plate coated with reaction-cured glass were measured across several conditions in the facility and compared with laminar and fully-turbulent CFD simulations. The potential for bypass transition in the PTF nozzle was assessed via application of the Langtry-Menter four-equation transitional shear-stress transport (SST) model. Results from the transition model were inconsistent with measurements. Flow interaction with a boundary conditioning plate feature inside the nozzle was also investigated as a potential source of laminar-to-turbulent transition using two turbulence models with specified transition locations. The Baldwin-Lomax turbulence model was configured to simulate a transition at the upstream edge of the boundary conditioning plate and produced results consistent with the surface pressure measurements but not the cold-wall heat flux. Finally, the SST turbulence model was calibrated to transition at the upstream edge of the boundary conditioning plate and produced results consistent with both the surface pressure and cold-wall heat flux measurements. The SST-based model demonstrated reasonable agreement with surface temperature measurements on the reaction-cured glass tile, albeit with some discrepancies.

Computational Fluid Dynamics↗

NASA NTRSDate not supplied

Toward Verification of the γ-Reθt Transition Model in OVERFLOW and FUN3D

The results of an ongoing assessment of the transition modeling capability in NASA's OVERFLOW and FUN3D programs are presented, with a focus on the Langtry-Menter γ-Reθt transition model in combination with the shear-stress transport (SST) turbulence model. While the effect of numerics and boundary conditions on the accuracy and iterative convergence of RANS solutions for fully turbulent flows has been well documented, especially in the context of canonical flow configurations, the same cannot be said for transport-equation-based transition models coupled with RANS-based turbulence models. Given the criticality of transition modeling for new aircraft design and optimization, there has been a renewed focus on the accuracy of such transition models and their inconsistent implementation across different flow solvers as seen from the AIAA and NATO-AVT workshops. In this work, we aim to establish the verification of such models via these two well established CFD codes with different numerics. The goal is to produce high-quality data, such as grids, solutions, and other auxiliary data, that may be utilized for code verification by others in the CFD community. As a first step, the work reported here is focused on the Langtry-Menter transition model as applied to two simple 2D configurations, namely the flat plate, and the NLF-0416, respectively. The paper also highlights how the boundary conditions and baseline turbulence model can affect the solutions from the SST-based Langtry-Menter transition model. A preliminary evaluation of the automatic mesh adaption capabilities of these solvers and potential benefits for flow configurations involving a mix of laminar, transitional, and fully turbulent flows is also reported.

CFD Modeling↗

NASA NTRSDate not supplied

Implementation of Two Local Correlation-Based Transition Models in OVERFLOW 2.3e

Accurate prediction of the laminar-to-turbulent boundary layer transition is highlighted as a vital component of NASA's CFD Vision 2030 Study. With an increased emphasis on greener air transports and sustainable aviation, transition modeling is anticipated to have an added significance, particularly in the applications related to laminar flow technology. However, unmanned aerial vehicles, crewed reentry vehicles, and ground-to-flight extrapolation all benefit from transition models. It is useful to incorporate a variety of models in CFD solvers because there isn't a single transition model that is ideal for the complete spectrum of applications. While the Langtry-Menter γ–Reθt model has been widely used for CFD predictions of flows with laminar, transitional, and turbulent boundary layers, it does not meet the criteria for Galilean invariance, a desirable attribute for rotorcraft applications. To help overcome that limitation, we have implemented Menter's SST-based γ transition model within NASA’s OVERFLOW Overset CFD code (version 2.3e). In addition, an SA-based implementation of the Langtry-Menter γ–Reθt transition model has also been implemented in view of the increased robustness of the SA-turbulence model for external aerodynamic applications. An initial assessment of the implemented models has been carried out using benchmark 2D test cases involving flat plates and the NLF-0416 airfoil, focusing on bypass, Tollmien-Schlichting, and laminar separation bubble-induced transition scenarios. In comparison to the Langtry-Menter γ–Reθt model, both models were found to produce increased computation efficiency, principally as a result of the decrease from four to three auxiliary transport equations. Results from the initial analysis will be presented, along with additional details pertaining to the deployment of these models.

CFD modeling↗

DOE OSTI2020

Low Temperature Aggregation Transitions in N3 and Y6 Acceptors Enable Double‐Annealing Method That Yields Hierarchical Morphology and Superior Efficiency in Nonfullerene Organic Solar Cells

Abstract Thermal transition of organic solar cells (OSCs) constituent materials are often insufficiently researched, resulting in trial‐and‐error rather than rational approaches to annealing strategies to improve domain purity to enhance the power conversion efficiency. Despite the potential utility, little is known about the thermal transitions of the modern high‐performance acceptors Y6 and N3. Here, by using an optical method, it is discovered that the acceptor N3 has a clear solid‐state aggregation transition at 82 °C. This unusually low transition not only explains prior optimization protocols, but the transition informs and enables a double‐annealing method that can fine‐tune aggregation and the device morphology. Compared with 16.6% efficiency for PM6:N3:PC 71 BM control devices, higher efficiency of 17.6% is obtained through the improved protocol. Morphology characterization with x‐ray scattering methods reveals the formation of a multilength scale morphology. Moreover, the double‐annealing method is illustrated and easily transferred and validated with Y6‐based devices, using the transition of Y6 at 102 °C. As a result, the PCE improved from 16.0% to 16.8%. Design of high‐performance acceptors with yet lower aggregation transitions might be required for OSCs to successfully transition to low thermal budget industrial processing methods where annealing temperatures on plastic substrates have to be kept low.

Qin, Yunpeng↗

DOE OSTI2026

Joint Optimization of Multimodal Transit Frequency and Shared Autonomous Vehicle Fleet Size with Hybrid Metaheuristic and Nonlinear Programming

Shared autonomous vehicles (SAVs) bring competition to traditional transit services but redesigning multimodal transit network can utilize SAVs as feeders to enhance service efficiency and coverage. This paper presents an optimization framework for the joint multimodal transit frequency and SAV fleet size problem, a variant of the transit network frequency setting problem. The objective is to maximize total transit ridership (including SAV-fed trips and subtracting boarding rejections) across multiple time periods under budget constraints, considering endogenous mode choice (transit, point-to-point SAVs, driving) and route selection, while allowing for strategic route removal by setting frequencies to zero. Due to the problem’s non-linear, non-convex nature and the computational challenges of large-scale networks, we develop a hybrid solution approach that combines a metaheuristic approach (particle swarm optimization) with nonlinear programming for local solution refinement. To ensure computational tractability, the framework integrates analytical approximation models for SAV waiting times based on fleet utilization, multimodal network assignment for route choice, and multinomial logit mode choice behavior, bypassing the need for computationally intensive simulations within the main optimization loop. Applied to the Chicago metropolitan area’s multimodal network, our method illustrates a 33.3% increase in transit ridership through optimized transit route frequencies and SAV integration, particularly enhancing off-peak service accessibility and strategically reallocating resources.

Ng, Max↗

DOE OSTI2020

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications. This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2 H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature T g can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in T g and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of T g with increased confinement that is strongly influenced by the pore-liquid interface characteristics. This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. Finally, while the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Navigating Transition-Metal Chemical Space: Artificial Intelligence for First-Principles Design

Conspectus The variability of chemical bonding in open-shell transition-metal complexes not only motivates their study as functional materials and catalysts but also challenges conventional computational modeling tools. Here, tailoring ligand chemistry can alter preferred spin or oxidation states as well as electronic structure properties and reactivity, creating vast regions of chemical space to explore when designing new materials atom by atom. Although first-principles density functional theory (DFT) remains the workhorse of computational chemistry in mechanism deduction and property prediction, it is of limited use here. DFT is both far too computationally costly for widespread exploration of transition-metal chemical space and also prone to inaccuracies that limit its predictive performance for localized d electrons in transition-metal complexes. These challenges starkly contrast with the well-trodden regions of small-organic-molecule chemical space, where the analytical forms of molecular mechanics force fields and semiempirical theories have for decades accelerated the discovery of new molecules, accurate DFT functional performance has been demonstrated, and gold-standard methods from correlated wavefunction theory can predict experimental results to chemical accuracy. The combined promise of transition-metal chemical space exploration and lack of established tools has mandated a distinct approach. In this Account, we outline the path we charted in exploration of transition-metal chemical space starting from the first machine learning (ML) models (i.e., artificial neural network and kernel ridge regression) and representations for the prediction of open-shell transition-metal complex properties. The distinct importance of the immediate coordination environment of the metal center as well as the lack of low-level methods to accurately predict structural properties in this coordination environment first motivated and then benefited from these ML models and representations. Once developed, the recipe for prediction of geometric, spin state, and redox potential properties was straightforwardly extended to a diverse range of other properties, including in catalysis, computational “feasibility”, and the gas separation properties of periodic metal–organic frameworks. Interpretation of selected features most important for model prediction revealed new ways to encapsulate design rules and confirmed that models were robustly mapping essential structure–property relationships. Encountering the special challenge of ensuring that good model performance could generalize to new discovery targets motivated investigation of how to best carry out model uncertainty quantification. Distance-based approaches, whether in model latent space or in carefully engineered feature space, provided intuitive measures of the domain of applicability. With all of these pieces together, ML can be harnessed as an engine to tackle the large-scale exploration of transition-metal chemical space needed to satisfy multiple objectives using efficient global optimization methods. In practical terms, bringing these artificial intelligence tools to bear on the problems of transition-metal chemical space exploration has resulted in ML-model assessments of large, multimillion compound spaces in minutes and validated new design leads in weeks instead of decades.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Quantized resistance revealed at the criticality of the quantum anomalous Hall phase transitions

In multilayered magnetic topological insulator structures, magnetization reversal processes can drive topological phase transitions between quantum anomalous Hall, axion insulator, and normal insulator states. Here we report an examination of the critical behavior of two such transitions: the quantum anomalous Hall to normal insulator (QAH-NI), and quantum anomalous Hall to axion insulator (QAH-AXI) transitions. By introducing a new analysis protocol wherein temperature dependent variations in the magnetic coercivity are accounted for, the critical behavior of the QAH-NI and QAH-AXI transitions are evaluated over a wide range of temperature and magnetic field. Despite the uniqueness of these different transitions, quantized longitudinal resistance and Hall conductance are observed at criticality in both cases. Furthermore, critical exponents were extracted for QAH-AXI transitions occurring at magnetization reversals of two different magnetic layers. The observation of consistent critical exponents and resistances in each case, independent of the magnetic layer details, demonstrates critical behaviors in quantum anomalous Hall transitions to be of electronic rather than magnetic origin. Our finding offers a new avenue for studies of phase transition and criticality in QAH insulators.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗