Insights into the role of the H-abstraction reaction kinetics of amines in understanding their degeneration fates under atmospheric and combustion conditions.

Amines, a class of prototypical volatile organic compounds, have garnered considerable interest within the context of atmospheric and combustion chemistry due to their substantial contributions to the formation of hazardous pollutants in the atmosphere. In the current energy landscape, the implementation of carbon-neutral energy and strategic initiatives leads to generation of new amine sources that cannot be overlooked in terms of the emission scale. To reduce the emission level of amines from their sources and mitigate their impact on the formation of harmful substances, a comprehensive understanding of the fundamental reaction kinetics during the degeneration process of amines is imperative. This perspective article first presents an overview of both traditional amine sources and emerging amine sources within the context of carbon peaking and carbon neutrality and then highlights the importance of H-abstraction reactions in understanding the atmospheric and combustion chemistry of amines from the perspective of reaction kinetics. Subsequently, the current experimental and theoretical techniques for investigating the H-abstraction reactions of amines are introduced, and a concise summary of research endeavors made in this field over the past few decades is provided. In order to provide accurate kinetic parameters of the H-abstraction reactions of amines, advanced kinetic calculations are performed using the multi-path canonical variational theory combined with the small-curvature tunneling and specific-reaction parameter methods. By comparing with the literature data, current kinetic calculations are comprehensively evaluated, and these validated data are valuable for the development of the reaction mechanism of amines.

Theoretical Study on Ethylamine Dissociation Reactions Using VRC-VTST and SS-QRRK Methods.

Barrierless bond dissociation reactions play an important role in fuel combustion. In this work, the pressure-dependent dissociation rate constants of ethylamine (EA) are accurately determined using variable-reaction-coordinate variational transition-state theory combined with the system-specific quantum Rice-Ramsperger-Kassel method. Before the kinetics calculations, the performances of four density functional theory methods in describing the bond dissociation of EA are evaluated against the benchmark method, FIC-MRCISD(T)+Q/cc-pVTZ, and the MN15-L/cc-pVTZ method is the best choice. By comparison of the Gibbs free energies and the rate constants for the bond dissociation reactions of EA, ethanol, and propane, the influence of functional groups on the reaction kinetics is discussed. The kinetics calculations show that the dissociation rate constants of EA are sensitive to pressure at low pressures and high temperatures, and the dominant channel is the reaction that yields C2H5 and NH2 radicals. A literature combustion model of EA is updated with our calculations, and the satisfactory agreement between the model predictions and reported ignition delay times of EA suggests the reliability of our calculations.

Ultrafast X-Ray Diffraction Visualization of B1-B2 Phase Transition in KCl under Shock Compression.

The classical B1(NaCl)↔B2(CsCl) transitions have been considered as a model for general structural phase transformations, and resolving corresponding phase transition mechanisms under high strain rate shock compression is critical to a fundamental understanding of phase transition dynamics. Here, we use subnanosecond synchrotron x-ray diffraction to visualize the lattice response of single-crystal KCl to planar shock compression. Complete B1-B2 orientation relations are revealed for KCl under shock compression along ⟨100⟩_{B1} and ⟨110⟩_{B1}; the orientation relations and transition mechanisms are anisotropic and can be described with the standard and modified Watanabe-Tokonami-Morimoto model, respectively, both involving interlayer sliding and intralayer ion rearrangement. The current study also establishes a paradigm for investigating solid-solid phase transitions under dynamic extremes with ultrafast synchrotron x-ray diffraction.

Full strain tensor measurements with X-ray diffraction and strain field mapping: a simulation study.

Strain tensor measurements are important for understanding elastic and plastic deformation, but full bulk strain tensor measurement techniques are still lacking, in particular for dynamic loading. Here, such a methodology is reported, combining imaging-based strain field mapping and simultaneous X-ray diffraction for four typical loading modes: one-dimensional strain/stress compression/tension. Strain field mapping resolves two in-plane principal strains, and X-ray diffraction analysis yields volumetric strain, and thus the out-of-plane principal strain. This methodology is validated against direct molecular dynamics simulations on nanocrystalline tantalum. This methodology can be implemented with simultaneous X-ray diffraction and digital image correlation in synchrotron radiation or free-electron laser experiments.

Deducing density and strength of nanocrystalline Ta and diamond under extreme conditions from X-ray diffraction.

In situ X-ray diffraction with advanced X-ray sources offers unique opportunities for investigating materials properties under extreme conditions such as shock-wave loading. Here, Singh's theory for deducing high-pressure density and strength from two-dimensional (2D) diffraction patterns is rigorously examined with large-scale molecular dynamics simulations of isothermal compression and shock-wave compression. Two representative solids are explored: nanocrystalline Ta and diamond. Analysis of simulated 2D X-ray diffraction patterns is compared against direct molecular dynamics simulation results. Singh's method is highly accurate for density measurement (within 1%) and reasonable for strength measurement (within 10%), and can be used for such measurements on nanocrystalline and polycrystalline solids under extreme conditions (e.g. in the megabar regime).

Capture Deformation Twinning in Mg during Shock Compression with Ultrafast Synchrotron X-Ray Diffraction.

Deformation twinning plays a vital role in accommodating plastic deformation of hexagonal-close-packed (hcp) metals, but its mechanisms are still unsettled under high strain rate shock compression. Here we investigate deformation twinning in shock-compressed Mg as a typical hcp metal with in situ, ultrafast synchrotron x-ray diffraction. Extension twinning occurs upon shock compression along ⟨112[over ¯]0⟩ and ⟨101[over ¯]0⟩, but only upon release for loading along ⟨0001⟩. Such deformation mechanisms are a result of the polarity of deformation twinning, which depends on directionality and relative magnitude of resolved shear stress and may be common for Mg and its alloys in a wide range of strain rates.

GAPD: a GPU-accelerated atom-based polychromatic diffraction simulation code.

GAPD, a graphics-processing-unit (GPU)-accelerated atom-based polychromatic diffraction simulation code for direct, kinematics-based, simulations of X-ray/electron diffraction of large-scale atomic systems with mono-/polychromatic beams and arbitrary plane detector geometries, is presented. This code implements GPU parallel computation via both real- and reciprocal-space decompositions. With GAPD, direct simulations are performed of the reciprocal lattice node of ultralarge systems (∼5 billion atoms) and diffraction patterns of single-crystal and polycrystalline configurations with mono- and polychromatic X-ray beams (including synchrotron undulator sources), and validation, benchmark and application cases are presented.

Simulations of X-ray diffraction of shock-compressed single-crystal tantalum with synchrotron undulator sources.

Polychromatic synchrotron undulator X-ray sources are useful for ultrafast single-crystal diffraction under shock compression. Here, simulations of X-ray diffraction of shock-compressed single-crystal tantalum with realistic undulator sources are reported, based on large-scale molecular dynamics simulations. Purely elastic deformation, elastic-plastic two-wave structure, and severe plastic deformation under different impact velocities are explored, as well as an edge release case. Transmission-mode diffraction simulations consider crystallographic orientation, loading direction, incident beam direction, X-ray spectrum bandwidth and realistic detector size. Diffraction patterns and reciprocal space nodes are obtained from atomic configurations for different loading (elastic and plastic) and detection conditions, and interpretation of the diffraction patterns is discussed.

Balancing strength, hardness and ductility of Cu64Zr36 nanoglasses via embedded nanocrystals.

Superplasticity can be achieved in nanoglasses but at the expense of strength, and such a loss can be mitigated via embedding stronger nanocrystals, i.e., forming nanoglass/nanocrystal composites. As an illustrative case, we investigate plastic deformation of Cu64Zr36 nanoglass/nanocrystalline Cu composites during uniaxial tension and nanoindentation tests with molecular dynamics simulations. With an increasing fraction of nanocrystalline grains, the tensile strength of the composite is enhanced, while its ductility decreases. The dominant interface type changes from a glass-glass interface to glass-crystal interface to grain boundary, corresponding to a failure mode transition from superplastic flow to shear banding to brittle intercrystal fracture, respectively. Accordingly, the indentation hardness increases continuously and strain localization beneath the indenter is more and more severe. For an appropriate fraction of nanocrystalline grains, a good balance among strength, hardness and ductility can be realized, which is useful for the synthesis of novel nanograined glass/crystalline composites with high strength, high hardness and superior ductility.

Theoretical Investigation on Hydrogen Abstraction by NO2 from Symmetric Ethers (CH3)2 xO ( x = 1-4).

Hydrogen abstractions by NO2 from symmetric ethers are investigated to determine the rate constants and explore the effect of the functional group on rate constants at different reaction sites. The involved ethers are dimethyl ether (DME), diethyl ether (DEE), dipropyl ether (DPE), and dibutyl ether (DBE). The B3LYP method with a 6-31G(2df,p) basis set is employed to optimize the ground-state geometries and for frequency and intrinsic reaction coordinate calculations. The G4 method is used to calculate the electronic energies for the small ethers (DME and DEE). Given the heavy computational cost of the G4 method, the modified G4MP2 method is applied for larger ethers (DPE and DBE) and also for DME to verify the accuracy of the G4MP2 method by benchmarking with the G4 method. The high-pressure limit rate constants are calculated within the temperature range of 500-2000 K, with the asymmetrical Eckart tunneling correction as well as one-dimensional hindered rotor treatment. The calculated rate constants agree well with the literature data, and the branch ratio analysis suggests that the cis-HONO channel basically dominates the hydrogen abstraction reactions and shows a decrease at high temperatures, followed by HNO2 and trans-HONO channels; in addition, the hydrogen abstraction at the C site adjacent to the ether bond (α reaction site) accounts for most of the reactions. Furthermore, the total rate constants of the ethers are compared to those of their half-structurally alkanes, and linear Bell-Evans-Polanyi correlations are observed.

Crystallization of Lennard-Jones liquids under dynamic compression: Heterogeneous and homogeneous nucleation.

We investigate crystallization of Lennard-Jones liquids on substrates under dynamic compression with large-scale molecular dynamics simulations. The substrates examined include single crystals and bicrystals with different crystallographic orientations, and the loading paths include shock and quasi-isentropic loading. Microstructure is characterized with simulated x-ray diffraction and orientation mapping. For shock loading, only heterogeneous nucleation occurs at the simulation scales. Quasi-isentropic loading induces less heating and larger supercooling; as a result, heterogeneous nucleation occurs at low loading strengths, and both heterogeneous and homogeneous nucleation occur at high loading strengths, despite the crystalline substrates. Crystallization depends on the substrate structure (crystal orientation and grain boundary) and loading characteristics. Deformation may induce grain structure change (e.g., reorientation and twinning) of substrates and affect subsequent crystallization. Crystallization rate is anisotropic, inversely proportional to the cosine of the dihedral angle between the substrate plane and a main {111} growth plane.

Dynamic crystal rotation resolved by high-speed synchrotron X-ray Laue diffraction.

Dynamic compression experiments are performed on single-crystal Si under split Hopkinson pressure bar loading, together with simultaneous high-speed (250-350 ns resolution) synchrotron X-ray Laue diffraction and phase-contrast imaging. A methodology is presented which determines crystal rotation parameters, i.e. instantaneous rotation axes and angles, from two unindexed Laue diffraction spots. Two-dimensional translation is obtained from dynamic imaging by a single camera. High-speed motion of crystals, including translation and rotation, can be tracked in real time via simultaneous imaging and diffraction.

Unraveling Photoinduced Spin Dynamics in the Topological Insulator Bi(2)Se(3).

We report on a time-resolved ultrafast optical spectroscopy study of the topological insulator Bi_{2}Se_{3}. We unravel that a net spin polarization cannot only be generated using circularly polarized light via interband transitions between topological surface states (SSs), but also via transitions between SSs and bulk states. Our experiment demonstrates that tuning photon energy or temperature can essentially allow for photoexcitation of spin-polarized electrons to unoccupied topological SSs with two distinct spin relaxation times (∼25 and ∼300 fs), depending on the coupling between SSs and bulk states. The intrinsic mechanism leading to such distinctive spin dynamics is the scattering in SSs and bulk states which is dominated by E_{g}^{2} and A_{1g}^{1} phonon modes, respectively. These findings are suggestive of novel ways to manipulate the photoinduced coherent spins in topological insulators.

Macrodeformation Twins in Single-Crystal Aluminum.

Deformation twinning in pure aluminum has been considered to be a unique property of nanostructured aluminum. A lingering mystery is whether deformation twinning occurs in coarse-grained or single-crystal aluminum at scales beyond nanotwins. Here, we present the first experimental demonstration of macrodeformation twins in single-crystal aluminum formed under an ultrahigh strain rate (∼10^{6} s^{-1}) and large shear strain (200%) via dynamic equal channel angular pressing. Large-scale molecular dynamics simulations suggest that the frustration of subsonic dislocation motion leads to transonic deformation twinning. Deformation twinning is rooted in the rate dependences of dislocation motion and twinning, which are coupled, complementary processes during severe plastic deformation under ultrahigh strain rates.

Improved ductility of Cu64Zr36 metallic glass/Cu nanocomposites via phase and grain boundaries.

We investigate tensile deformation of metallic glass/crystalline interpenetrating phase nanocomposites as regards the effects of specific area of amorphous/crystalline phase interfaces, and grain boundaries. As an illustrative case, large-scale molecular dynamics simulations are performed on Cu64Zr36 metallic glass/Cu nanocomposites with different specific interface areas and grain boundary characteristics. Plastic deformation is achieved via shear bands, shear transformation zones, and crystal plasticity. Three-dimensional amorphous/crystalline interfaces serve as effective barriers to the propagation of shear transformation zones and shear bands if formed, diffuse strain localizations, and give rise to improved ductility. Ductility increases with increasing specific interface area. In addition, introducing grain boundaries into the second phase facilitates crystal plasticity, which helps reduce or eliminate mature shear bands in the glass matrix.

Crystallization in supercooled liquid Cu: Homogeneous nucleation and growth.

Homogeneous nucleation and growth during crystallization of supercooled liquid Cu are investigated with molecular dynamics simulations, and the microstructure is characterized with one- and two-dimensional x-ray diffraction. The resulting solids are single-crystal or nanocrystalline, containing various defects such as stacking faults, twins, fivefold twins, and grain boundaries; the microstructure is subject to thermal fluctuations and extent of supercooling. Fivefold twins form via sequential twinning from the solid-liquid interfaces. Critical nucleus size and nucleation rate at 31% supercooling are obtained from statistical runs with the mean first-passage time and survival probability methods, and are about 14 atoms and 10(32) m(-3)s(-1), respectively. The bulk growth dynamics are analyzed with the Johnson-Mehl-Avrami law and manifest three stages; the Avrami exponent varies in the range of 1-19, which also depends on thermal fluctuations and supercooling.

Thermally driven grain boundary migration and melting in Cu.

With molecular dynamics simulations, we systematically investigate melting of a set of Σ3〈110〉70.53° tilt grain boundaries (GB) in Cu bicrystals, including coherent twin boundaries (CTBs), 12 asymmetric tilt grain boundaries (ATGBs), and symmetric incoherent twin boundaries (SITBs), in the order of increasing length weight of SITB or GB energy. ATGBs decompose into CTBs and SITBs, which migrate and coalesce as a result of internal stress relaxation. GBs can be superheated or premelted, and GB melting temperature decreases exponentially with increasing SITB weight, owing to the systematics in GB microstructure. GB melting nucleates at disordered CTB-SITB junctions, and grows along SITBs and then into grain interiors, with the solid-liquid interfaces preferentially aligned with {111}.

Cavitation in a metallic liquid: homogeneous nucleation and growth of nanovoids.

Large-scale molecular dynamics (MD) simulations are performed to investigate homogeneous nucleation and growth of nanovoids during cavitation in liquid Cu. We characterize in detail the atomistic cavitation processes by following the temporal evolution of cavities or voids, analyze the nucleation behavior with the mean first-passage time (MFPT) and survival probability (SP) methods, and discuss the results against classical nucleation theory (CNT), the Tolman equation for surface energy, independent calculation of surface tension via integrating the stress profiles, the Johnson-Mehl-Avrami (JMA) growth law, and the power law for nucleus size distributions. Cavitation in this representative metallic liquid is a high energy barrier Poisson processes, and the steady-state nucleation rates obtained from statistical runs with the MFPT and SP methods are in agreement. The MFPT method also yields the critical nucleus size and the Zeldovich factor. Fitting with the Tolman's equation to the MD simulations yields the surface energy of a planar interface (~0.9 J m⁻²) and the Tolman length (0.4-0.5 Å), and those values are in accord with those from integrating the stress profiles of a planar interface. Independent CNT predictions of the nucleation rate (10(33 - 34) s(-1) m(-3)) and critical size (3-4 Å in radius) are in agreement with the MFPT and SP results. The JMA law can reasonably describe the nucleation and growth process. The size distribution of subcritical nuclei appears to follow a power law with an exponent decreasing with increasing tension owing to coupled nucleation and growth, and that of the supercritical nuclei becomes flattened during further stress relaxation due to void coalescence.

Local and bulk melting of shocked columnar nanocrystalline Cu: Dynamics, anisotropy, premelting, superheating, supercooling, and re-crystallization.

We perform large-scale molecular dynamics simulations to study shock-induced melting transition of idealized hexagonal columnar nanocrystalline Cu. The as-constructed nanocrystalline Cu consists of unrotated (reference) and rotated columnar crystals, relative to the columnar axis. Shock loading is applied along three principal directions of the columnar Cu: two transverse (zigzag and armchair) and one longitudinal directions. Dynamic local melting processes are highly anisotropic with respect to the shock directions. For the transverse directions, hotspot effect and disparate dynamic responses of grains with different orientations may lead to partial or complete premelting of the initially rotated grains, which in turn leads to transient supercooling and heterogeneous recrystallization, and thus, the formation of nanocrystalline solids with modified grain structures or solid-liquid mixtures, depending on the extent of supercooling. With increasing shock strengths, the reference grains melt heterogeneously at interfaces and homogeneously inside. Conversely, "bulk" premelting of the rotated grains is absent for the longitudinal direction, except for grain boundary melting. The progression of recrystallization or heterogenous melting diminishes and eventually eliminates the transient premelting or superheating of the system via latent heat and thermal diffusion. Premelting or superheating appears unlikely for bulk melting or well-defined Hugoniot states, if the thermal and mechanical equilibria are achieved, and the thermodynamic melting curve coincides with the partial melting Hugoniot states of a polycrystalline solid.

Shock response of single crystal and nanocrystalline pentaerythritol tetranitrate: Implications to hotspot formation in energetic materials.

We investigate shock response of single crystal and nanocrystalline pentaerythritol tetranitrate (PETN) with a coarse-grained model and molecular dynamics simulations, as regards mechanical hotspot formation in the absence or presence of grain boundaries (GBs). Single crystals with different orientations, and columnar nanocrystalline PETN with regular hexagonal, irregular hexagonal, and random GB patterns, are subjected to shock loading at different shock strengths. In single crystals, shock-induced plasticity is consistent with resolved shear stress calculations and the steric hindrance model, and this deformation leads to local heating. For regular-shaped hexagonal columnar nanocrystalline PETN, different misorientation angles lead to activation of different/same slip systems, different deformation in individual grains and as a whole, different GB friction, different temperature distributions, and then, different hotspot characteristics. Compared to their regular-shaped hexagonal counterpart, nanocrystalline PETN with irregular hexagonal GB pattern and that with random GBs, show deformation and hotspot features specific to their GBs. Driven by stress concentration, hotspot formation is directly related to GB friction and GB-initiated crystal plasticity, and the exact deformation is dictated by grain orientations and resolved shear stresses. GB friction alone can induce hotspots, but the hotspot temperature can be enhanced if it is coupled with GB-initiated crystal plasticity, and the slip of GB atoms has components out of the GB plane. The magnitude of shearing can correlate well with temperature, but the slip direction of GB atoms relative to GBs may play a critical role. Wave propagation through varying microstructure may also induce differences in stress states (e.g., stress concentrations) and loading rates, and thus, local temperature rise. GB-related friction and plasticity induce local heating or mechanical hotspots, which could be precursors to chemical hotspot formation related to initiation in energetic materials, in the absence of other, likely more effective, means for hotspot formation such as void collapse.