Mechanistic Transition Research Articles

Combining formal methods and Bayesian approach for inferring discrete-state stochastic models from steady-state data

Stochastic population models are widely used to model phenomena in different areas such as cyber-physical systems, chemical kinetics, collective animal behaviour, and beyond. Quantitative analysis of stochastic population models easily becomes challenging due to the combinatorial number of possible states of the population. Moreover, while the modeller easily hypothesises the mechanistic aspects of the model, the quantitative parameters associated to these mechanistic transitions are difficult or impossible to measure directly. In this paper, we investigate how formal verification methods can aid parameter inference for population discrete-time Markov chains in a scenario where only a limited sample of population-level data measurements—sample distributions among terminal states—are available. We first discuss the parameter identifiability and uncertainty quantification in this setup, as well as how the existing techniques of formal parameter synthesis and Bayesian inference apply. Then, we propose and implement four different methods, three of which incorporate formal parameter synthesis as a pre-computation step. We empirically evaluate the performance of the proposed methods over four representative case studies. We find that our proposed methods incorporating formal parameter synthesis as a pre-computation step allow us to significantly enhance the accuracy, precision, and scalability of inference. Specifically, in the case of unidentifiable parameters, we accurately capture the subspace of parameters which is data-compliant at a desired confidence level.

Bending the rules: Strain accommodation in layered crystalline solids through nanoscale buckling over dislocations

Basal dislocations and ripplocations both offer explanations for the deformation of layered crystalline solids in response to compressive strain. Existing work, however, presents no clear definition of a ripplocation and the distinction between these two mechanisms remains unclear. Molecular dynamics simulations in graphite and modified graphitic models reveal that equivalent additional half-planes of material can induce both dislocations and ripplocations. In this work, we find that ripplocations are essentially an elastic buckling phenomenon operating at the atomic scale, rather than a discrete crystallographic defect. Dislocation core confinement produces incommensurate planar elastic strains with sufficient energy to trigger a buckling instability that transfers strain energy to the surrounding lattice. The interplay between incommensurate strain and buckling is a quasi-continuum phenomenon where both mechanisms may accommodate arbitrary disregistry, not only the discrete values accommodated by perfect or partial basal dislocations. The mechanistic transition depends critically on the atomic-scale interfacial energies between layers and the continuum elastic behavior of the bulk material. Buckling is possible, though unfavorable, in the MAX phase Ti3AlC2 and systems of multiple layers buckle at lower strains than only a single layer. These extensions of the ripplocation model in van der Waals layered solids suggest that nanoscale elastic buckling potentially plays a role in the deformation of a wide range of layered crystalline systems in response to common mechanical configurations.

Stabilizing Cobalt‐free Li‐rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two‐phase Ru Doping

AbstractThe application of Li‐rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt‐free Li1.2Ni0.2Mn0.6O2 and demonstrates the positive impact of two‐phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2Ni0.2Mn0.6O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post‐mortem synchrotron analyses. The two‐phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2−) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity‐retention rate during long‐term cycling. The understanding of the structure‐function relationship of Li1.2Ni0.2Mn0.6O2 sheds light on the selective doping strategy and rational materials design for better‐performance Li‐rich layered oxides.

Stabilizing Cobalt-free Li-rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two-phase Ru Doping.

The application of Li-rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt-free Li1.2 Ni0.2 Mn0.6 O2 and demonstrates the positive impact of two-phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2 Ni0.2 Mn0.6 O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post-mortem synchrotron analyses. The two-phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2- ) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity-retention rate during long-term cycling. The understanding of the structure-function relationship of Li1.2 Ni0.2 Mn0.6 O2 sheds light on the selective doping strategy and rational materials design for better-performance Li-rich layered oxides.

Unraveling relative roles of bulk precipitation and surface growth in developing a scaling layer in membrane distillation

Scaling of sparingly soluble salts is a challenge standing in the way of enhancing water recovery of desalination via an approach based on membrane distillation (MD). Improvement of anti-scaling strategies is dependent on understanding various mechanisms accounting for evolution of the scaling layer. This study made efforts to address a fundamental concern as to how bulk precipitation is competing with surface growth to form a layer of crystalline particles in the process of MD. When concentrating a feed containing calcium sulfate, scaling was induced in a series of MD processes with a varied transmembrane temperature difference. In addition to the measurements of flux decline and electrical conductivity, optical coherence tomography (OCT) was explored to simultaneously monitor the formation of crystals in the feed bulk and resolve the scaling layer evolving on the membrane surface. Comparison of these characterization results revealed the key role of surface growth in initiating the scaling, while suggesting that the cake development could be gradually dominated by the deposition of crystals formed in the feed bulk. A further analysis of the local growth rates provided deeper insights into the mechanistic transition; effects of varying the degree of supersaturation were also discussed in the context of redistributing the size of deposits and inducing the crystal-membrane interactions. This study refines the picture of developing a scaling layer in MD, which would be of great value in advancing applications of MD-based desalination.

Exploring the origins of the indentation size effect at submicron scales

The origin of the indentation size effect has been extensively researched over the last three decades, following the establishment of nanoindentation as a broadly used small-scale mechanical testing technique that enables hardness measurements at submicrometer scales. However, a mechanistic understanding of the indentation size effect based on direct experimental observations at the dislocation level remains limited due to difficulties in observing and quantifying the dislocation structures that form underneath indents using conventional microscopy techniques. Here, we employ precession electron beam diffraction microscopy to "look beneath the surface," revealing the dislocation characteristics (e.g., distribution and total length) as a function of indentation depth for a single crystal of nickel. At smaller depths, individual dislocation lines can be resolved, and the dislocation distribution is quite diffuse. The indentation size effect deviates from the Nix-Gao model and is controlled by dislocation source starvation, as the dislocations are very mobile and glide away from the indented zone, leaving behind a relatively low dislocation density in the plastically deformed volume. At larger depths, dislocations become highly entangled and self-arrange to form subgrain boundaries. In this depth range, the Nix-Gao model provides a rational description because the entanglements and subgrain boundaries effectively confine dislocation movement to a small hemispherical volume beneath the contact impression, leading to dislocation interaction hardening. The work highlights the critical role of dislocation structural development in the small-scale mechanistic transition in indentation size effect and its importance in understanding the plastic deformation of materials at the submicron scale.

Particle flattening during cold spray: Mechanistic regimes revealed by single particle impact tests

The flattening ratio, ε, is an important diagnostic measurement of particle deformability and coating quality assessment in cold spray. However, the experimental determination of ε and correlation of it to experimental parameters (particle size, velocity) is not straightforward from observations of cold-sprayed coatings. Here we present a series of direct site-specific measurements of ε for well-known particle sizes and velocities, without the many complications involved in a full cold spray experiment. This approach permits us to identify mechanistic transitions separating three apparent regimes of behavior. In regime I, at lower velocities just high enough to cause bonding, an impacting particle flattens largely unhindered. In regime II, at somewhat higher velocities, the substrate develops a significant crater, which in turn constrains lateral particle flattening as the particle burrows more deeply into the substrate. In regime III, at very high velocities, hydrodynamic particle penetration is observed, distinguished by deep burrowing of the particle, which adopts a concave-saucer shape, with large petals of substrate ejected backwards out of the surface. While direct measurements in regimes I and II show that deformed particles can be reasonably modeled as oblate spheroids, that assumption fails in regime III. To the extent that particle flattening is deemed desirable, this analysis suggests a more nuanced view of the velocities used in cold spray.

Catalytic Lewis and Brønsted acid syn-diastereoselective benzylic substitutions of α-hydroxy-β-nitro- and α-hydroxy-β-azido-alkyl arenes

A series of alkyl and alkenyl p-methoxy arenes containing α,β-disubstituted diamino and amino alcohol groups were synthesized from β-nitro and β-azido benzylic alcohols in the presence of AuCl3 as catalyst. The formation of predominantly syn-disubstituted products were rationalized on the basis of mechanistic considerations and transition state models relying on A1,3-allylic strain. The products could have utility in the design of medicinally relevant compounds and as chiral ligands for asymmetric catalysis. A new synthesis of (+)-sertraline (Zoloft) was achieved.

Calcite dissolution rates in seawater: Lab vs. in-situ measurements and inhibition by organic matter

Ocean acidification from fossil fuel burning is lowering the mean global ocean saturation state (Ω = Ca2+CO32−Ksp′), thus increasing the thermodynamic driving force for calcium carbonate minerals to dissolve. This dissolution process will eventually neutralize the input of anthropogenic CO2, but the relationship between Ω and calcite dissolution rates in seawater is still debated. Recent advances have also revealed that spectrophotometric measurements of seawater pHs, and therefore in-situ Ωs, are systematically lower than pHs/Ωs calculated from measurements of alkalinity (Alk) and total dissolved inorganic carbon (DIC). The location of the calcite saturation horizon, defined as the depth in the water column where Ω = 1, therefore shifts by ~5–10% depending on the parameters used to calculate Ω. The “true” saturation horizon remains unknown. To resolve these issues, we developed a new in-situ reactor and measured dissolution rates of 13C-labeled inorganic calcite at four stations across a transect of the North Pacific Ocean. In-situ saturation was calculated using both Alk-DIC (Ω(Alk, DIC)) and Alk-pH (Ω(Alk, pH)) pairs. We compare in-situ dissolution rates with rates measured in filtered, poisoned, UV-treated seawater at 5 and 21 °C under laboratory conditions. We observe in-situ dissolution above Ω(Alk, DIC) = 1, but not above Ω(Alk, pH) = 1. We emphasize that marine carbonate system equilibria should be reevaluated and that care should be taken when using proxies calibrated to historical Ω(Alk, DIC). Our results further demonstrate that calcite dissolution rates are slower in-situ than in the lab by a factor of ~4, but that they each possess similar reaction orders (n) when fit to the empirical Rate = k(1-Ω)n equation. The reaction orders are n < 1 for 0.8 < Ω < 1 and n = 4.7 for 0 < Ω < 0.8, with the kink in rates at Ωcrit = 0.8 being consistent with a mechanistic transition from step edge retreat to homogenous etch pit formation. We reconcile the offset between lab and in-situ rates by dissolving calcite in the presence of elevated orthophosphate (20 μm) and dissolved organic carbon (DOC) concentrations, where DOC is in the form of oxalic acid (20 μm), gallic acid (20 μm), and d-glucose (100 μm). We find that soluble reactive phosphate has no effect on calcite dissolution rates from pH 5.5–7.5, but the addition of DOC in the form of d-glucose and oxalic acid slows laboratory dissolution rates to match in-situ observations, potentially by inhibiting the retreat rate of steps on the calcite surface. Our lab and in-situ rate data form an envelope around previous in-situ dissolution measurements and may be considered outer bounds for dissolution rates in low/high DOC waters. The lower bound (high DOC) is most realistic for particles formed in, and sinking out of, surface waters, and is described by R(mol cm-2 s-1) = 10–14.3±0.2(1-Ω)0.11±0.1 for 0.8 < Ω < 1, and R(mol cm-2 s-1) = 10–10.8±0.4(1-Ω)4.7±0.7 for 0 < Ω < 0.8. These rate equations are derived from in-situ measurements and may be readily implemented into marine geochemical models to describe water column calcite dissolution.

Recruiting monomer for dimer formation: resolving the antagonistic mechanisms of novel immune check point inhibitors against Programmed Death Ligand-1 in cancer immunotherapy

ABSTRACTThe design of small molecule antagonists against Programmed Death Ligand-1 (PD-L1) has been the recent highlight of the immune checkpoint blockade therapy. This interventive approach has been potentiated by the development of BMS compounds; BMS-1001 and BMS-1166, which exert their therapeutic activities by inducing dimerisation of PD-L1; a molecular mechanism that has remained unclear. For the first time, we resolve the dynamical events that underlie the antagonistic mechanisms of BMS-1001 and BMS-1166 when bound to PD-L1 using an all-atom molecular dynamics (MD) simulations approach and free binding energy Molecular Mechanics/Poisson-Boltzmann Surface Area (MM/PBSA) calculations. Time-scale dynamical findings revealed that upon binding a PD-L1 monomer, the BMS-compounds gradually facilitated the ‘inbound’ motion of another PD-L1 monomer in the same conformational phase space up till dimer formation. Moreover, the non-liganded PD-L1 monomer exhibited the highest structural flexibility and atomistic motions relative to the BMS-liganded monomer as revealed by post-MD trajectory analyses using root mean square deviation (RMSD) and root mean square fluctuations (RMSF) parameters. Trajectory investigations into ligand motions also revealed that the BMS compounds exhibited mechanistic transitions from the monomeric binding site (monomer A) where they were initially bound, to the second monomeric site (monomer B) where they were strongly bound, followed by eventual high-affinity interactions at the tunnel-like binding cleft formed upon the dimerisation of both PD-L1 monomers. These findings present a model that describes the mechanism by which the BMS compounds induce PD-L1 dimerisation and could further enhance the design of highly selective and novel monomeric recruiters of PD-L1 in cancer immunotherapy.

Peptides as Bio-Inspired Electronic Materials: An Electrochemical and First-Principles Perspective.

Molecular electronics is at the forefront of interdisciplinary research, offering a significant extension of the capabilities of conventional silicon-based technology as well as providing a possible stand-alone alternative. Bio-inspired molecular electronics is a particularly intriguing paradigm, as charge transfer in proteins/peptides, for example, plays a critical role in the energy storage and conversion processes for all living organisms. However, the structure and conformation of even the simplest protein is extremely complex, and therefore, synthetic model peptides comprising well-defined geometry and predetermined functionality are ideal platforms to mimic nature for the elucidation of fundamental biological processes while also enhancing the design and development of single-peptide electronic components. In this Account, we first present intramolecular electron transfer within two synthetic peptides, one with a well-defined helical conformation and the other with a random geometry, using electrochemical techniques and computational simulations. This study reveals two definitive electron transfer pathways (mechanisms), the natures of which are dependent on secondary structure. Following on from this, electron transfer within a series of well-defined helical peptides, constrained by either Huisgen cycloaddition, ring-closing metathesis, or a lactam bridge, was determined. The electrochemical results indicate that each constrained peptide, in contrast to a linear counterpart, exhibits a remarkable shift of the formal potential to the positive (>460 mV) and a significant reduction of the electron transfer rate constant (up to 15-fold), which represent two distinct electronic "on/off" states. High-level calculations demonstrate that the additional backbone rigidity provided by the side-bridge constraints leads to an increased reorganization energy barrier, which impedes the vibrational fluctuations necessary for efficient intramolecular electron transfer through the peptide backbone. Further calculations reveal a clear mechanistic transition from hopping to superexchange (tunneling) stemming from side-bridge gating. We then extended our research to fine-tuning of the electronic properties of peptides through both structural and chemical manipulation, to reveal an interplay between electron-rich side chains and backbone rigidity on electron transfer. Further to this, we explored the possibility that the side-bridge constraints present in our synthetic peptides provide an additional electronic transport pathway, which led to the discovery of two distinct forms of quantum interferometer. The effects of destructive quantum interference appear essentially through both the backbone and an alternative tunneling pathway provided by the side bridge in the constrained β-strand peptide, as evidenced by a correlation between electrochemical measurements and conductance simulations for both linear and constrained β-strand peptides. In contrast, an interplay between quantum interference effects and vibrational fluctuations is revealed in the linear and constrained 310-helical peptides. Collectively, these exciting findings augment our fundamental knowledge of charge transfer dynamics and kinetics in peptides and also open up new avenues to design and develop functional bio-inspired electronic devices, such as on/off switches and quantum interferometers, for practical applications in molecular electronics.

Monitoring the Hydrothermal Growth of Cobalt Spinel Water Oxidation Catalysts: From Preparative History to Catalytic Activity.

The hydrothermal growth of cobalt oxide spinel (Co3 O4 ) nanocrystals from cobalt acetate precursors was monitored with in situ powder X-ray diffraction (PXRD) in combination with ex situ electron microscopy and vibrational spectroscopy. Kinetic data from in situ PXRD monitoring were analyzed using Sharp-Hancock and Gualtieri approaches, which both clearly indicate a change of the growth mechanism for reaction temperatures above 185 °C. This mechanistic transition goes hand in hand with morphology changes that notably influence the photocatalytic oxygen evolution activity. Complementary quenching investigations of conventional hydrothermal Co3 O4 growth demonstrate that these insights derived from in situ PXRD data provide valuable synthetic guidelines for water oxidation catalyst production. Furthermore, the ex situ analyses of hydrothermal quenching experiments were essential to assess the influence of amorphous cobalt-containing phases arising from the acetate precursor on the catalytic activity. Thereby, the efficient combination of a single in situ technique with ex situ analyses paves the way to optimize parameter-sensitive hydrothermal production processes of key energy materials.

Understanding the charge transport properties of redox active metal-organic conjugated wires.

Layer-by-layer assembly of the dirhodium complex [Rh2(O2CCH3)4] (Rh2) with linear N,N'-bidentate ligands pyrazine (LS) or 1,2-bis(4-pyridyl)ethene (LL) on a gold substrate has developed two series of redox active molecular wires, (Rh2LS) n @Au and (Rh2LL) n @Au (n = 1-6). By controlling the number of assembling cycles, the molecular wires in the two series vary systematically in length, as characterized by UV-vis spectroscopy, cyclic voltammetry and atomic force microscopy. The current-voltage characteristics recorded by conductive probe atomic force microscopy indicate a mechanistic transition for charge transport from voltage-driven to electrical field-driven in wires with n = 4, irrespective of the nature and length of the wires. Whilst weak length dependence of electrical resistance is observed for both series, (Rh2LL) n @Au wires exhibit smaller distance attenuation factors (β) in both the tunneling (β = 0.044 Å-1) and hopping (β = 0.003 Å-1) regimes, although in (Rh2LS) n @Au the electronic coupling between the adjacent Rh2 centers is stronger. DFT calculations reveal that these wires have a π-conjugated molecular backbone established through π(Rh2)-π(L) orbital interactions, and (Rh2LL) n @Au has a smaller energy gap between the filled π*(Rh2) and the empty π*(L) orbitals. Thus, for (Rh2LL) n @Au, electron hopping across the bridge is facilitated by the decreased metal to ligand charge transfer gap, while in (Rh2LS) n @Au the hopping pathway is disfavored likely due to the increased Coulomb repulsion. On this basis, we propose that the super-exchange tunneling and the underlying incoherent hopping are the dominant charge transport mechanisms for shorter (n ≤ 4) and longer (n > 4) wires, respectively, and the Rh2L subunits in mixed-valence states alternately arranged along the wire serve as the hopping sites.

Deconstructed Analogues of Bupropion Reveal Structural Requirements for Transporter Inhibition versus Substrate-Induced Neurotransmitter Release.

Bupropion (1), an α-aminophenone uptake inhibitor at plasma membrane transporters for dopamine (DAT) and norepinephrine (NET), is a widely prescribed antidepressant and smoking cessation aid. Cathinone (2), a structurally simpler α-aminophenone, is a substrate-type releasing agent at the same transporters and a recognized drug of abuse. Our goal was to identify the structural features of α-aminophenones that govern the mechanistic transition from uptake inhibition to substrate-induced release. Deconstructed analogues of 1 were synthesized and compared for their ability to interact with DAT, NET, and the serotonin transporter (SERT) using in vitro assay methods. Bulky amine substituents resulted in compounds that function as DAT uptake inhibitors but not release agents, whereas smaller amine substituents result in relatively nonselective releasing agents at DAT and NET. Our findings add to empirical evidence supporting distinct molecular determinants for α-aminophenone- (i.e., cathinone-) related agents acting as transporter inhibitors versus those acting as releasers.

A controllable mechanistic transition of charge transfer in helical peptides: from hopping to superexchange

A controllable mechanistic transition of charge transfer in helical peptides is demonstrated as a direct result of side-bridge gating.

Geometry-dependent compressive responses in nanoimprinted submicron-structured shape memory polyurethane.

High resolution surface textures, when rationally designed, provide an attractive surface engineering approach to enhance surface functionalities. Designing smart surfaces by coupling surface texture with shape memory polymers has garnered attention in achieving tunable mechanical properties. We investigate the structure-mechanical property relationships for programmable, shape-memorizing submicron-scale pillar arrays subjected to flat-punch compression. The geometrically-dependent deformation of structured surfaces with two different aspect ratios (250 nm-pillars 1 : 1 and 550 nm-pillars 2.4 : 1) were investigated, and their moduli were found to be lower than that of non-patterned surface. From finite element analysis, the pillar deformation is correlated to a mechanistic transition from a discrete, unidirectional compression of 250 nm-pillars to lateral constraints caused by interpillar contact in 550 nm-pillars. This lateral pillar-pillar contact in the 550 nm-pillars resulted in an increased and maximum strain-dependent modulus but lower elastic recovery and energy dissipation as compared with the 250 nm-pillars. Furthermore, the compressive responses of temporarily shaped pillars (programmed by stretching) were compared with the permanently shaped pillars. The extent of lateral constraints controlled by pillar shape and spacing in 550 nm-pillars was responsible for the modulus differences between the original and stretched patterns, whereas the modulus of 250 nm-pillars remained as a constant value with different levels of stretching. This study provides mechanistic insights into how the mechanical behavior can be modulated by designing the aspect ratio of shape memory pillar arrays and by programming the surface geometry, thus revealing the potential of developing ingenious designs of responsive surfaces sensitive to mechanical deformation.

Decay Mechanism of NO3(•) Radical in Highly Concentrated Nitrate and Nitric Acidic Solutions in the Absence and Presence of Hydrazine.

The decay mechanism of NO3(•) has been determined through a combination of experiment and calculation for 7 mol dm(-3) solutions of deaerated aqueous LiNO3 and HNO3, in the absence and presence of hydrazine (N2H4, N2H5(+), and N2H6(2+)). In the absence of hydrazine, the predominant NO3(•) decay pathways are strongly dependent upon the pH of the solution. For neat, neutral pH LiNO3 solutions (7 mol dm(-3)), NO3(•) produced by the pulse is fully consumed within 160 μs by OH(•) (37%), H2O (29%), NO2(-) (17%), and NO2 (17%). For acidic HNO3 solutions (7 mol dm(-3)), radiolytically produced NO3(•) is predominantly consumed within 1 ms by HNO2 (15%) and NO2 (80%). Intervening formulations exhibit the mechanistic transition from neat LiNO3 to neat HNO3. In highly acidic nitric acid solution, hydrazine exists mainly as N2H5(+) and N2H6(2+), both of which rapidly consume NO3(•) in addition to other decay mechanisms, with rate constants of 2.9 (±0.9) × 10(7) and 1.3 (±0.3) × 10(6) dm(3) mol(-1) s(-1), respectively.

Pivotal Role and Regulation of Proton Transfer in Water Oxidation on Hematite Photoanodes.

Hematite is a promising material for solar water splitting; however, high efficiency remains elusive because of the kinetic limitations of interfacial charge transfer. Here, we demonstrate the pivotal role of proton transfer in water oxidation on hematite photoanodes using photoelectrochemical (PEC) characterization, the H/D kinetic isotope effect (KIE), and electrochemical impedance spectroscopy (EIS). We observed a concerted proton-electron transfer (CPET) characteristic for the rate-determining interfacial hole transfer, where electron transfer (ET) from molecular water to a surface-trapped hole was accompanied by proton transfer (PT) to a solvent water molecule, demonstrating a substantial KIE (∼3.5). The temperature dependency of KIE revealed a highly flexible proton transfer channel along the hydrogen bond at the hematite/electrolyte interface. A mechanistic transition in the rate-determining step from CPET to ET occurred after OH(-) became the dominant hole acceptor. We further modified the proton-electron transfer sequence with appropriate proton acceptors (buffer bases) and achieved a greater than 4-fold increase in the PEC water oxidation efficiency on a hematite photoanode.

Mechanistic transition of heat conduction in two-dimensional solids: A study of silica bilayers

Thermal transport in solids changes its nature from phonon propagation that suffers from perturbative scattering to thermally activated hops between localized vibrational modes as the level of disorder increases. Models have been proposed to understand these two distinct extremes that predict opposite temperature dependence of the thermal conductivity but not for the transition or the intermediate regime. Here we explore thermal transport in two-dimensional silica with varying levels of disorder $\ensuremath{\alpha}$ by performing atomistic simulations, as well as analysis based on the kinetic and Allen-Feldman theories. We demonstrate a crossover between the crystalline and amorphous regimes at $\ensuremath{\alpha}\ensuremath{\sim}0.3$, which is characterized by a turnover of the temperature dependence in thermal conductivity and explained by the dominance of thermal hopping processes. This critical disorder level is also identified in the analysis of the participation ratio of localized vibrational modes and the spatial localization of heat flux. These factors serve as key indicators in quantitatively characterizing the mechanism of heat transport in the transitional regime.

Prediction of Growth Habit of β-Cyclotetramethylene-tetranitramine Crystals by the First-Principles Models

Experimentally, β-cyclotetramethylene-tetranitramine (β-HMX) crystals were found to dramatically elongate to the [100] direction when a relatively high supersaturation was imposed. A sudden growth of β-HMX to the [100] direction is closely associated with a mechanistic transition from spiral growth to two-dimensional (2D) nucleation for the (110) face. The onset supersaturation for the growth by 2D nucleation, σ2D, was found to play a key role in the growth of β-HMX. The present simulation results based on first-principles models such as the spiral growth model and the 2D nucleation model show that the values of σ2D on the (101) and (101) faces are smaller than those on the (020), (110), and (011) faces. This leads to the prediction of rapid growth rates for the (101) and (101) faces by 2D nucleation at low supersaturation and the appearance of a typical shape of β-HMX. On the other hand, the needle-like shape of β-HMX begins to prevail when the supersaturation exceeds the σ2D for the (110) face because...