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At least 271 records · Page 15

Understanding interfacial segregation in polymer blend films with random and mixed side chain bottlebrush copolymer additives

Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chain chemistries. Specifically, we synthesized bottlebrush polymers with either poly(styrene-ran-methyl methacrylate) side chains or with a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains. Furthermore, the bottlebrush additives were matched in terms of PS and PMMA compositions, and they were blended with linear PS or PMMA chains that ranged in length from shorter to longer than the bottlebrush side chains. Experiments revealed similar behaviors of the two types of bottlebrushes, with a slight preference for mixed side-chain bottlebrushes at the film surface. SCFT simulations were qualitatively consistent with experimental observations, predicting only slight differences in the segregation of bottlebrush additives driven by side chain microstructures. Specifically, these slight differences were driven by the chemistries of the bottlebrush polymer joints and side chain end-groups, which were entropically repelled and attracted to interfaces, respectively. Using SCFT, we also demonstrated that the interfacial behaviors were dominated by entropic effects with high molecular weight linear polymers, leading to enrichment of bottlebrush near interfaces. Surprisingly, the SCFT simulations showed that the chemistry of the joints connecting the bottlebrush backbones and side chains played a more significant role compared with the side chain end groups in affecting differences in surface excess of bottlebrushes with random and mixed side chains. This work provides new insights into the effects of side chain microstructure on segregation of bottlebrush polymer additives.

36 MATERIALS SCIENCE↗

Layered structures of assembled imine-linked macrocycles and two-dimensional covalent organic frameworks give rise to prolonged exciton lifetimes

Ordered organic materials and assemblies have great potential to be tailored to have desirable properties for optoelectronic applications, such as long exciton lifetime and high directional exciton mobility. Framework materials, such as two-dimensional covalent organic frameworks (2D COFs), as well as their truncated macrocyclic analogues, are versatile platforms to organize functional aromatic systems into designed assemblies and robust materials. In this study we investigate the exciton dynamics in a 2D COF, its corresponding hexagonal macrocycle, and extended nanotubes comprised of stacked macrocycles. The excitonic behavior of these three systems provide an understanding of excitonic processes that occur in the plane of the covalently bonded 2D macromolecules and between layers of the nanotubes and 2D COF. The nanotube and analogous 2D COF exhibit longer excited-state lifetimes (~100 ps) compared to the individual, solvated macrocycles (<0.5 ps). These differences are attributed to the internal conversion facilitated by the internal motions of the imine linkages which are significantly reduced in the assembled macrocycles in the nanotube and 2D COF sheets in the layered structures. The exciton diffusion processes in the assembled nanotubes and 2D COF systems were characterized by the autocorrelations of the transition dipole moment of the excitons, giving the depolarization time constants for both systems to be ~1 ps. This work also reveals the anisotropic exciton dynamics related to the in-plane and inter-plane structural factors in these systems. These studies provide guidance for the design of future COF materials, where the longer excited state lifetimes imparted by assembly are beneficial for optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing the SEI formation between lithium metal and solid-state electrolyte

The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li 3 PS 4 interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li 3 PS 4 . This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (~40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li 3 PS 4 interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li 2 S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. Finally, this information is crucial for better understanding interfacial ion mobility.

25 ENERGY STORAGE↗

Effects of catholyte aging on high-nickel NMC cathodes in sulfide all-solid-state batteries

Sulfide solid-state electrolytes (SSEs) in all-solid-state batteries (SSBs) are recognized for their high ionic conductivity and inherent safety. The LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode offers a high thermodynamic potential of approximately 3.8 V vs. Li/Li + and a theoretical specific capacity of 200 mA h g −1 . However, the practical utilization of NMC811 in sulfide SSBs faces significant interfacial challenges. The oxidation instability of sulfide solid electrolytes against NMC811 and the formation of the cathode electrolyte interphase (CEI) during cycling lead to degradation and reduced cell performance. Volumetric changes in NMC during lithiation and de-lithiation can also cause detachment from sulfide electrolytes or internal particle cracking. Despite extensive galvanostatic cycling studies to address the issues, the calendar life of sulfide SSBs remains poorly understood. Here, we systematically studied the effects of four different catholytes on the calendar aging of LiNbO 3 (LNO)-coated NMC811, including Li 6 PS 5 Cl (LPSCl), Li 3 InCl 6 –Li 6 PS 5 Cl (LIC–LPSCl), Li 3 YCl 6 –Li 6 PS 5 Cl (LYC–LPSCl), and Li 10 GeP 2 S 12 (LGPS). Our results indicate that LPSCl provides optimal capacity retention when stored at high state-of-charge (SOC) at room temperature, but the LIC–LPSCl cathode shows significant capacity degradation and chemical incompatibility. We also established an effective electrochemical calendar aging testing protocol to simulate daily usage, enabling quick inference of the calendar life of SSBs. In conclusion, this new testing approach accelerates materials selection strategies for high-nickel NMC composite cathodes in sulfide SSBs.

25 ENERGY STORAGE↗

Elucidating Norrish type I reactive pathways by ultrafast X-ray absorption spectroscopy

Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.

Graßl, Martin [SLAC National Accelerator Laborator↗

Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ∼1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ∼100 cm−1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Dynamic strain evolution in an optically excited Pt thin film

The structural evolution of a Pt thin film following photo-thermal excitation by 1 ps optical laser pulses was studied with a time resolution of 100 ps over a total time period of 1 ms. Laser pulse fluences below 50 mJ/cm 2 were insufficient to relax the residual stress state of the as-prepared film even after 10 000 pulses. In this fluence regime, a rapid initial lattice expansion and a decrease in the lattice coherence length due to ultrafast photo-thermal heating were observed. The lattice expansion reached a maximum, and the coherence length reached a minimum, 100–200 ps after excitation before monotonically decaying back to their initial values in about 1 µs. Laser pulse fluences greater than 50 mJ/cm 2 produced irreversible stress relaxation within the first 10 optical pulses. In this regime, the lattice expansion was qualitatively similar to that in the low fluence regime, except that the initial structural state was not recovered. The evolution in the coherence length, however, was more complex. Following an initial decrease similar to that observed at low fluence, the coherence length then increased to a broad maximum greater than the initial value, before recovery.

36 MATERIALS SCIENCE↗

Phase transitions in Zr at sub-nanosecond time scales

Here solid-solid phase transitions are investigated in Zr thin films using shock compression induced by a short laser pulse (<1 ns). Shock wave profiles are measured at free surfaces for films of different thicknesses (a few micrometers) using chirped-pulse line velocimetry with 10 ps time resolution. Experiments are performed at pressures up to ~50 GPa, which is sufficient to reach the ω and β phases under equilibrium conditions. The shock wave structures are analyzed using a general Lagrangian analysis method, which allows for the calculation of stress–strain paths and assessments of phase transition behavior. In agreement with recent short laser pulse experiments using ultra-fast x-ray diffraction, we do not find any clear evidence of the α–ω transition, though this would be expected from the phase diagram. Instead, we infer a direct transformation to a metastable β-phase at lower shock pressures (<20 GPa) and equilibrium β at higher pressures. Through the velocimetry analysis, we find α–β transformation onset times of less than ~100 ps and completion times of less than ~200 ps.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Experimental verification of TNSA protons and deuterons in the multi-picosecond moderate intensity regime

Ion acceleration from high intensity short pulse laser interactions is of great interest due to a number of applications, and there has been significant work carried out with laser energies up to a few 100 J with 10's of femtosecond to 1 ps pulse durations. Here, we report results from an experiment at the OMEGA EP laser, where laser energy and pulse length were varied from 100 to 1250 J and 0.7–30 ps, respectively, in the moderate (2 × 10 17 –2 × 10 18 W/cm 2 ) laser intensity regime. Ions and electrons were simultaneously measured from disk targets made of CH and CD by a Thomson parabola and a magnetic spectrometer, respectively. Measurements showed that the electron temperature, T e (MeV), has a dependence on the laser energy, E L (J), and pulse duration, τ L (ps), and its empirical scaling was found to be 0.015 × E L 0.90 τ L –0.48. The maximum proton and deuteron energies are linearly dependent on the electron temperature, (5.60 ± 0.26) × T e and (3.17 ± 0.18) × T e , respectively. A significant increase in proton numbers with the laser energy was also observed. Furthermore, the increase in the maximum proton energy and proton count with higher energy longer duration pulses presented in this article shows that such laser conditions have a great advantage for applications, such as the proton radiograph, in the moderate laser intensity regime.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Introduction to the special topic on inertial confinement fusion diagnostics

In the first decade of the 21st century, the United States began operating three leading Inertial Confinement Fusion (ICF) and High-Energy Density Physics (HEDP) facilities. The National Ignition Facility (NIF) began its quest to first surpass the Lawson Criterion and then reach thermonuclear ignition and thermonuclear gain. The Omega EP (Extended Performance) laser provides unprecedented energy, reliability, and consistency for petawatt (PW)-class laser experiments. The Omega laser continues to support over 1000 ICF and HEDP experiments each year. The Z pulsed power machine is a Z-pinch plasma confinement device that was refurbished to increase current drive and improve reliability. The extreme states of matter created in these new facilities required advancement of many technologies. The most important among these was the significant improvement in instrumentation capabilities needed to diagnose plasma conditions and resulting nuclear products. The instruments needed a better temporal, spatial, and energy resolution. They also needed to be hardened against EMP and radiation. Typical events in an ICF implosion include compressing the deuterium–tritium (DT) fuel to greater than 60 g/cm 3 and heating the DT to a temperature greater than 10 keV (110 000 000 K). The DT atoms react to produce 14 MeV neutrons from a volume with a radius of ~30 μm. When the fuel ignites, the DT burn prop agates into cold fuel and the neutron-emitting region can reach sizes of over 200 μm. Furthermore, the burn typically lasts less than 150 ps, but the burn duration will decrease as the DT yield increases. Burn durations as short as 90 ps have been recorded and are predicted to decrease still further to 20 ps. X-ray imaging diagnostics are needed to measure the acceleration and velocity of the capsule enclosing the DT, where the implosion velocities can reach over 400 km/s.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Imaging the photochemistry of cyclobutanone using ultrafast electron diffraction: Experimental results

We investigated the ultrafast structural dynamics of cyclobutanone following photoexcitation at λ = 200 nm using gas-phase megaelectronvolt ultrafast electron diffraction. Our investigation complements the simulation studies of the same process within this special issue. It provides information about both electronic state population and structural dynamics through well-separable inelastic and elastic electron scattering signatures. We observe the depopulation of the photoexcited S 2 state of cyclobutanone with n3s Rydberg character through its inelastic electron scattering signature with a time constant of (0.29 ± 0.2) ps toward the S 1 state. The S 1 state population undergoes ring-opening via a Norrish Type-I reaction, likely while passing through a conical intersection with S 0 . The corresponding structural changes can be tracked by elastic electron scattering signatures. These changes appear with a delay of (0.14 ± 0.05) ps with respect to the initial photoexcitation, which is less than the S 2 depopulation time constant. This behavior provides evidence for the ballistic nature of the ring-opening once the S 1 state is reached. The resulting biradical species react further within (1.2 ± 0.2) ps via two rival fragmentation channels yielding ketene and ethylene, or propene and carbon monoxide. Furthermore, our study showcases the value of both gas-phase ultrafast diffraction studies as an experimental benchmark for nonadiabatic dynamics simulation methods and the limits in the interpretation of such experimental data without comparison with such simulations.

Carbon monoxide↗

Low-mode nonuniformity in direct-drive ICF implosions due to laser smoothing techniques employed on OMEGA

For successful laser-direct-drive inertial confinement fusion implosions, the laser irradiation must be highly uniform over the target surface. On OMEGA, multiple laser beams are used to illuminate targets quasi-uniformly. High-mode-number nonuniformities due to laser speckle on each individual beam are reduced by splitting each beam into two orthogonal polarizations (i.e., polarization smoothing, or PS) and a range of wavelengths (i.e., smoothing by spectral dispersion) that are dispersed at the target plane. However, cross-beam energy transfer (CBET) is sensitive to both the polarizations and wavelengths of the interacting beams, so the interplay between CBET and the laser-smoothing schemes results in unique intensity variation across each beam profile, which is a systematic source of low-mode drive nonuniformity on OMEGA. Here, we model these effects and find that the predicted ℓ = 1 mode in the laser-absorption distribution is consistent with the systematic core-flow direction that has been determined from the OMEGA implosion database. We also observe good agreement with the measured core-flow directions for two specific sets of implosions (one with PS, the other without PS) when we also account for the measured beam mispointing and the beam power imbalance.

Crossed beam scattering↗

Development and scaling of MeV x-ray radiography at NIF-ARC

We investigate the generation of MeV x-rays using the Advanced Radiography Capability laser system at the National Ignition Facility using 1, 10, and 38 ps pulse durations, with laser energies reaching up to 4 kJ and using compound parabolic concentrators. Hydrodynamic simulations using up-to-date measurements of the contrast of the ARC laser are conducted, allowing us to employ an electron scaling model that incorporates scale length and pulse duration, which aligns closely with the observed temperature distributions. Comparable x-ray sources, in terms of dose, are generated when using a 10 ps pulse duration with 2.4 kJ at ∼1.9 ± 0.4 × 10 18 W/cm 2 and when using a 38 ps pulse duration with 4 kJ at 9.9 ± 0.4 × 10 17 W/cm 2 , both achieving ∼16 rad in air at 1 m for x-ray energies > 0.5 MeV. Radiographs performed on the laser “line-of-sight” show significant improvements in image quality than radiographs performed at 65 degrees to the laser axis. We verify the radiography performance using Monte Carlo Simulations.

Physics - Plasma physics↗

Light-induced H 2 generation in a photosystem I-O 2 -tolerant [FeFe] hydrogenase nanoconstruct

The fusion of hydrogenases and photosynthetic reaction centers (RCs) has proven to be a promising strategy for the production of sustainable biofuels. Type I (iron-sulfur-containing) RCs, acting as photosensitizers, are capable of promoting electrons to a redox state that can be exploited by hydrogenases for the reduction of protons to dihydrogen (H 2 ). While both [FeFe] and [NiFe] hydrogenases have been used successfully, they tend to be limited due to either O 2 sensitivity, binding specificity, or H 2 production rates. In this study, we fuse a peripheral (stromal) subunit of Photosystem I (PS I), PsaE, to an O 2 -tolerant [FeFe] hydrogenase from Clostridium beijerinckii using a flexible [GGS] 4 linker group (CbHydA1-PsaE). We demonstrate that the CbHydA1 chimera can be synthetically activated in vitro to show bidirectional activity and that it can be quantitatively bound to a PS I variant lacking the PsaE subunit. When illuminated in an anaerobic environment, the nanoconstruct generates H 2 at a rate of 84.9 ± 3.1 µmol H 2 mg chl –1 h –1 . Further, when prepared and illuminated in the presence of O 2 , the nanoconstruct retains the ability to generate H 2 , though at a diminished rate of 2.2 ± 0.5 µmol H 2 mg chl –1 h –1 . This demonstrates not only that PsaE is a promising scaffold for PS I-based nanoconstructs, but the use of an O 2 -tolerant [FeFe] hydrogenase opens the possibility for an in vivo H 2 generating system that can function in the presence of O 2 .

Hydrogenase↗

Revealing charge carrier dynamics and transport in Te-doped GaAsSb and GaAsSbN nanowires by correlating ultrafast terahertz spectroscopy and optoelectronic characterization

Recent advances in the growth of III-V semiconductor nanowires (NWs) hold great promise for nanoscale optoelectronic device applications. It is established that a small amount of nitrogen (N) incorporation in III-V semiconductor NWs can effectively red-shift their wavelength of operation and tailor their electronic properties for specific applications. Still, understanding the impact of N incorporation on non-equilibrium charge carrier dynamics and transport in semiconducting NWs is critical in achieving efficient semiconducting NW devices. In this work, ultrafast optical pump-terahertz probe spectroscopy has been used to study non-equilibrium carrier dynamics and transport in Te-doped GaAsSb and dilute nitride GaAsSbN NWs, with the goal of correlating these results with electrical characterization of their equilibrium photo-response under bias and low-frequency noise characteristics. Nitrogen incorporation in GaAsSb NWs led to a significant increase in the carrier scattering rate, resulting in a severe reduction in carrier mobility. Carrier recombination lifetimes of 33 ± 1 picoseconds (ps) and 147 ± 3 ps in GaAsSbN and GaAsSb NWs, respectively, were measured. The reduction in the carrier lifetime and photoinduced optical conductivities are due to the presence of N-induced defects, leading to deterioration in the electrical and optical characteristics of dilute nitride NWs relative to the non-nitride NWs. Finally, we observed a very fast rise time of ~2 ps for both NW materials, directly impacting their potential use as high-speed photodetectors.

36 MATERIALS SCIENCE↗

Redshift space power spectrum beyond Einstein-de Sitter kernels

Abstract We develop a framework to compute the redshift space power spectrum (PS), with kernels beyond Einstein-de Sitter (EdS), that can be applied to a wide variety of generalized cosmologies. We build upon a formalism that was recently employed for standard cosmology in Chen, Vlah & White (2020), and utilize an expansion of the density-weighted velocity moment generating function that explicitly separates the magnitude of the k-modes and their angle to the line-of-sight direction dependencies. We compute the PS for matter and biased tracers to 1-loop Perturbation Theory (PT) and show that the expansion has a correct infrared and ultraviolet behavior, free of unwanted divergences. We also add Effective Field Theory (EFT) counterterms, necessary to account for small-scale contributions to PT, and employ an IR-resummation prescription to properly model the smearing of the BAO due to large scale bulk flows within Standard-PT. To demonstrate the applicability of our formalism, we apply it on the ΛCDM and the Hu-Sawicki f(R) models, and compare our numerical results against the elephant suite of N-body simulations, finding very good agreement up to k = 0.27 Mpc -1 h at z = 0.5 for the first three non-vanishing Legendre multipoles of the PS. To our knowledge, the model presented in this work is the most accurate theoretical EFT-PT for modified gravity to date, being the only one that accounts for beyond linear local biasing in redshift-space. Hence, we argue our RSD modeling is a promising tool to construct theoretical templates in order to test deviations from ΛCDM using real data obtained from the next stage of cosmological surveys such as DESI and LSST.

Astronomy & Astrophysics↗

Magnetic shear effect on plasma transport at T e / T i ~ 1 through electron cyclotron heating in DIII-D plasmas

The effect of magnetic shear on plasma transport for an electron to ion temperature ratio ( T e / T i ) near unity has been explored in DIII-D utilizing electron cyclotron heating (ECH). Previous reports showed that significant confinement degradation occurred at T e / T i ~ 1 in positive shear (PS) plasmas in DIII-D, whereas reduced confinement degradation was observed in negative central shear (NCS) plasmas. In this study, plasma transport in weak magnetic shear (WS) plasmas with ECH is investigated and compared with that in NCS and PS plasmas. Here the magnetic shears ($\hat s$) are $\hat s$ > 0.5, ~0 and <-0.1 in the core region (ρ~ 0.3–0.4) of PS, WS and NCS plasmas, respectively, and flat or negative inside ρ~ 0.4 in the WS and NCS plasmas. Weak magnetic shear is found to be effective in minimizing degradation of ion thermal confinement as T e / T i increases through ECH application, and an improved confinement factor of H 98y2 ~ 1.2 is maintained, similar to NCS plasmas. At T e / T i ~ 1, the ion thermal diffusivity around an internal transport barrier decreases when changing the magnetic shear from positive to weak or negative shear. Also, reduced local particle and momentum transport was indicated by steeper density and toroidal rotation profiles in the weak and negative shear regimes. Linear gyrokinetic simulations predict little change in growth rates of low-k turbulence with ECH application in the WS and NCS plasmas, which is consistent with the transport and profile analyses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗