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At least 1,351 records · Page 75

Electronic Structure and Dynamics of Higher-Lying Excited States in Light Harvesting Complex 1 from Rhodobacter sphaeroides

Light harvesting in photosynthetic organisms involves efficient transfer of energy from peripheral antenna complexes to core antenna complexes, and ultimately to the reaction center where charge separation drives downstream photosynthetic processes. Antenna complexes contain many strongly coupled chromophores, which complicates analysis of their electronic structure. Two-dimensional electronic spectroscopy (2DES) provides information on energetic coupling and ultrafast energy transfer dynamics, making the technique well suited for the study of photosynthetic antennae. Here in this paper, we present 2DES results on excited state properties and dynamics of a core antenna complex, light harvesting complex 1 (LH1), embedded in the photosynthetic membrane of Rhodobacter sphaeroides . The experiment reveals weakly allowed higher-lying excited states in LH1 at 770 nm, which transfer energy to the strongly allowed states at 875 nm with a lifetime of 40 fs. The presence of higher-lying excited states is in agreement with effective Hamiltonians constructed using parameters from crystal structures and atomic force microscopy (AFM) studies. The energy transfer dynamics between the higher- and lower-lying excited states agree with Redfield theory calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Entropy-Driven Porous Liquids Allowing Gas Solubility in Solvent-Filled Imine-Based Porous Organic Cages

Porous liquids offer a promising platform for gas separation by combining fluid processability with intrinsic molecular porosity. Traditional Type II porous liquids are formed by dissolving porous molecular cages in size-excluded solvents, limiting solvent options and practical applications. In this work, we introduce a novel method of creating Type II porous liquids using common small solvents, where intrinsic porosity is achieved at elevated pressures due to the selective displacement of solvent molecules by gas molecules within the cage structures. Using molecular simulations, we investigate the behavior of CO 2 in solutions of the imine-based porous organic cage CC13 dissolved in small molecular solvents such as chloroform and 1,2-dimethoxyethane (DME). Grand canonical Monte Carlo simulations of solid-state CC13 reveal that selectivity reversal, where smaller CO 2 molecules displace larger solvent molecules inside the cage, is achievable at sufficiently high pressures. Temperature quench molecular dynamics simulations confirm that while CO 2 displacement within chloroform-filled cages is limited, DME enables entropy-driven cage CO 2 occupancy at pressures as low as ∼23 bar, setting up the foundation of an alternative way of forming Type II porous liquids.

adsorption↗

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. In this paper, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3 NH 3 PbI 3–x Cl x ) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmission microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. Finally, these results show that PL probes effectively the species near or at the film surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing Hydrated Polymers via Dielectric Relaxation Spectroscopy: Connecting Relative Permittivity, State of Water, and Salt Transport Properties of Sulfonated Polysulfones

Sulfonated polysulfone is a promising membrane material for separation and energy generation processes that rely on membranes to control the rates of small-molecule (e.g., water and ions) transport. The interactions among water molecules, ions, and the sulfonate groups in these polymers play a key role in controlling these rates of transport, but much remains unknown about these fundamental interactions in sulfonated polymers. In this study, we used dielectric relaxation spectroscopy to characterize water molecule dynamics in sulfonated polysulfone and Nafion. We found that the charged sulfonate groups contribute to a restriction of water molecule dynamics (i.e., a reduction in the characteristic time scale of dipolar motions) in a manner that is governed by the concentration and nature (i.e., conjugate base strength) of the sulfonate group. Additionally, we develop strategies to use these data to aid in modeling ion transport in sulfonated polysulfone. These results may be useful to guide engineering strategies for polymeric membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microfluidic, One-Batch Synthesis of Pd Nanocrystals on N-Doped Carbon in Surfactant-Free Deep Eutectic Solvents for Formic Acid Electrochemical Oxidation

One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. In this work, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of similar to ~13 ± 3.5 nm and a high ESCA of 46.0 m 2 /g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of the Anionic Zinc-Adeninate Metal–Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal–organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust and Elastic Polymer Membranes with Tunable Properties for Gas Separation

Here, polymer membranes with the capability to process a massive volume of gas are especially attractive for practical applications of gas separation. Although much effort has been devoted to develop novel polymer membranes with increased selectivity, the overall gas-separation performance and lifetime of membrane are still negatively affected by the weak mechanical performance, low plasticization resistance and poor physical aging tolerance. Recently, elastic polymer membranes with tunable mechanical properties have been attracting significant attentions due to their tremendous potential applications. Herein, we report a series of urethanerich PDMS-based polymer networks (U-PDMS-NW) with improved mechanical performance for gas separation. The cross-link density of U-PDMS-NWs is tailored by varying the molecular weight ( M n ) of PDMS. The U-PDMS-NWs show up to 400% elongation and tunable Young’s modulus (1.3–122.2 MPa), ultimate tensile strength (1.1–14.3 MPa), and toughness (0.7–24.9 MJ/m 3 ). All of the U-PDMS-NWs exhibit salient gas-separation performance with excellent thermal resistance and aging tolerance, high gas permeability (>100 Barrer), and tunable gas selectivity (up to α[ P CO 2 / P N 2 ] ≈ 41 and α[ P CO 2 / P CH 4 ] ≈ 16). With well-controlled mechanical properties and gas-separation performance, these U-PDMS-NW can be used as a polymermembrane platform not only for gas separation but also for other applications such as microfluidic channels and stretchable electronic devices.

36 MATERIALS SCIENCE↗

Assessment of Different Application Grades of Post-Consumer Recycled (PCR) Polyolefins from Material Recovery Facilities (MRFs) in the United States

The recycling of plastics has been gaining traction in the following years as many companies, organizations, and governments are pushing toward a more circular economy. However, plastic recycling rates are still small compared to those of plastic production, especially for polyolefins, such as high-density polyethylene (HDPE) and polypropylene (PP). With the goal of finding applications for recycled plastic resin, recyclers can face some challenges associated with the heterogeneity in the polymer properties of plastic waste streams, which could hinder the full potential of recycling due to the lack of a consistent feedstock. Here, this study assessed how an additional sorting step of recycled HDPE and PP streams, separating them into two categories based on the previous application, impacts the recycled polymer properties, such as physical, molecular, and thermal. It was demonstrated that manually separating HDPE articles previously processed by extrusion blow molding (EBM) or injection molding (IM) and PP articles by thermoforming (TF) or IM could yield recycled resins with more consistent properties, considering the significant differences between them. This highlights that an additional sorting step would allow recyclers to target more premium or currently unattainable plastic processing applications with postconsumer recycled (PCR) resins, which could significantly promote an increase in plastic recycling rates. Nevertheless, the development of new technologies is needed to automate this extra sorting step, as with the increase in scale manual sortation could not be feasible and cost-effective, reducing the attractiveness of using PCR resins in comparison to virgin ones.

36 MATERIALS SCIENCE↗

Techno-Economic Analysis and Life Cycle Assessment of the Production of Biodegradable Polyaliphatic–Polyaromatic Polyesters

Poly(butylene-adipate terephthalate) (PBAT) is a polyaliphatic–polyaromatic polyester that is biodegradable and has found application in several markets, making it a widely produced biodegradable polymer worldwide. However, the production of PBAT is carbon-intensive, as it relies on the use of petroleum-based monomers. There is, thus, significant interest in identifying polyesters that are biodegradable and less carbon-intensive (e.g., use of biomass- derived monomers). In this work, we develop a detailed process model (and an associated database) for the production of polyaliphatic–polyaromatic polyesters including petroleum-based PBAT and biomass-derived alternatives including poly(pentylene- adipate terephthalate) and poly(pentylene-adipate furandicarboxy- late). Techno-economic analysis (TEA) reveals that the production costs of these polyesters strongly depend on monomer costs (accounting for over 90% of the total production cost) and identifies market conditions under which biomass-based polyesters can be cost-competitive to petroleum-based PBAT. Life cycle assessment (LCA) shows that biomass-derived polyesters can reduce the global warming impact of PBAT by half. Altogether, the proposed TEA/LCA model aims to provide guidance into polyesters that are most promising and help assess their overall economic and environmental performance.

42 ENGINEERING↗

Demand Response Operation of Electricity-Intensive Chemical Processes for Reduced Greenhouse Gas Emissions: Application to an Air Separation Unit

A recent push for reduced greenhouse gas (GHG) emissions has led (in part) to the addition of renewable electricity generation sources to the power generation mix. Renewables such as wind and solar are desynchronized from grid demand, requiring the use of fossil fuels to bridge the gap. We propose a novel production scheduling formulation, emissions-minimizing production (EMP), which utilizes time-based information on the nature of the power generation mix to lower GHG emissions related to the transmission and generation of electricity for industrial users. We demonstrate the application of EMP on a single-column air separation unit. The scheduling problem is cast as a mixed integer linear program that can be solved in a practical amount of time. Extensive numerical studies are used to place EMP in the context of other production scheduling methods (such as demand response), and demonstrate its potential for significant reductions in GHG emissions.

24 POWER TRANSMISSION AND DISTRIBUTION↗

A multi-step nucleation process determines the kinetics of prion-like domain phase separation

Compartmentalization by liquid-liquid phase separation (LLPS) has emerged as a ubiquitous mechanism underlying the organization of biomolecules in space and time. Here, we combine rapid-mixing time-resolved small-angle X-ray scattering (SAXS) approaches to characterize the assembly kinetics of a prototypical prion-like domain with equilibrium techniques that characterize its phase boundaries and the size distribution of clusters prior to phase separation. We find two kinetic regimes on the micro- to millisecond timescale that are distinguished by the size distribution of clusters. At the nanoscale, small complexes are formed with low affinity. After initial unfavorable complex assembly, additional monomers are added with higher affinity. At the mesoscale, assembly resembles classical homogeneous nucleation. Careful multi-pronged characterization is required for the understanding of condensate assembly mechanisms and will promote understanding of how the kinetics of biological phase separation is encoded in biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗

Theoretical prediction and atomic kinetic Monte Carlo simulations of void superlattice self-organization under irradiation

Nano-structured superlattices may have novel physical properties and irradiation is a powerful mean to drive their self-organization. However, the formation mechanism of superlattice under irradiation is still open for debate. Here we use atomic kinetic Monte Carlo simulations in conjunction with a theoretical analysis to understand and predict the self-organization of nano-void superlattices under irradiation, which have been observed in various types of materials for more than 40 years but yet to be well understood. The superlattice is found to be a result of spontaneous precipitation of voids from the matrix, a process similar to phase separation in regular solid solution, with the symmetry dictated by anisotropic materials properties such as one-dimensional interstitial atom diffusion. This discovery challenges the widely accepted empirical rule of the coherency between the superlattice and host matrix crystal lattice. The atomic scale perspective has enabled a new theoretical analysis to successfully predict the superlattice parameters, which are in good agreement with independent experiments. The theory developed in this work can provide guidelines for designing target experiments to tailor desired microstructure under irradiation. Furthermore, it may also be generalized for situations beyond irradiation, such as spontaneous phase separation with reaction.

36 MATERIALS SCIENCE↗

Carbon nanotube nanofluidics

Fluid flow under extreme spatial confinement exhibits unusual physical behaviors. This nanofluidic transport regime is relevant to a variety of mass transport, separation, and energy production processes in biological and industrial systems. Carbon nanotubes (CNTs) offer a nearly ideal platform for exploring nanofluidic transport because of their extremely narrow, smooth, hydrophobic inner pores, which enable very fast molecular flow while providing strong selectivity. In this review, we aim to provide a comprehensive understanding of nanofluidics in CNTs, focusing on the basic physics of mass transport in CNTs, various experimental platforms developed to investigate these phenomena, and key results on the permeation of water, protons, and ions. We focus on the critical factors that influence transport efficiency and selectivity, such as slip flow and charge regulation in CNTs, and the roles of entrance effects, dehydration processes and ion–charge interactions at the CNT entrances. We also explore the confinement effects, highlighting how the unique one-dimensional structure of CNTs imposes distinct constraints on fluid behavior and leads to novel single-file transport phenomena. Finally, we address current challenges and future directions of CNT nanofluidics.

Li, Zhongwu [Lawrence Livermore National Laborator↗

GaAs quantum dot solar cell under concentrated radiation

Effects of concentrated solar radiation on photovoltaic performance are investigated in well-developed GaAs quantum dot (QD) solar cells with 1-Sun efficiencies of 18%–19%. In these devices, the conversion processes are enhanced by nanoscale potential barriers and/or AlGaAs atomically thin barriers around QDs, which prevent photoelectron capture to QDs. Under concentrated radiation, the short circuit current increases proportionally to the concentration and the open circuit voltage shows the logarithmic increase. In the range up to hundred Suns, the contributions of QDs to the photocurrent are proportional to the light concentration. The ideality factors of 1.1–1.3 found from the V{sub OC}-Sun characteristics demonstrate effective suppression of recombination processes in barrier-separated QDs. The conversion efficiency shows the wide maximum in the range of 40–90 Suns and reaches 21.6%. Detailed analysis of I-V-Sun characteristics shows that at low intensities, the series resistance decreases inversely proportional to the concentration and, at ∼40 Suns, reaches the plateau determined mainly by the front contact resistance. Improvement of contact resistance would increase efficiency to above 24% at thousand Suns.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Growth far from equilibrium: Examples from III-V semiconductors

The development of new applications has driven the field of materials design and synthesis to investigate materials that are not thermodynamically stable phases. Materials which are not thermodynamically stable can be synthesized and used in many applications. These materials are kinetically stabilized during use. The formation of such metastable materials requires both an understanding of the associated thermochemistry and the key surface transport processes present during growth. Phase separation is most easily accomplished at the growth surface during synthesis where mass transport is most rapid. These surface transport processes are sensitive to the surface stoichiometry, reconstruction, and chemistry as well as the growth temperature. The formation of new metastable semiconducting alloys with compositions deep within a compositional miscibility gap serves as model systems for the understanding of the surface chemical and physical processes controlling their formation. The GaAs{sub 1−y}Bi{sub y} system is used here to elucidate the role of surface chemistry in the formation of a homogeneous metastable composition during the chemical vapor deposition of the alloy system.

36 MATERIALS SCIENCE↗

Aqueous density fractionation of nanocarbons from colliding-wave PBX9502 detonation soot

The study of solid carbon (nanocarbon) nucleation and growth from detonating high explosives is limited because of the difficulty directly evaluating chemical reactions behind the shock front. Understanding the correlation between detonation conditions and nanocarbon formation requires isolation, purification, and analysis of the carbon products. Aqueous density fractionation of products recovered from a colliding wave TATB-based high explosive (PBX9502) detonation are evaluated as an environmentally benign, “green” chemical processing approach for the separation of carbon materials from metal and metal oxide byproducts. Recovery of material sufficient for X-ray scattering analysis was obtained in two fractions. X-ray scattering showed the less dense fraction (ρ < 1 g/cm 3 ) contains hollow spherical core (d avg = 27.8 nm) nanoparticles with a shell (thickness=3.6 nm) composed of predominately sp 2 hybridized carbon. Particles contained within the dense fraction (ρ > 1 g/cm 3 ) were a mixture of oblate spheroids (major axis length=43.8 nm and minor axis=2.9 nm) and small polydisperse solid spherical particles (d avg = 2.4 nm) composed of both sp 2 and sp 3 bonded carbon with residual contamination from the brass detonators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

$\rm {H\,\small {I}}$ constraints from the cross-correlation of eBOSS galaxies and Green Bank Telescope intensity maps

We present the joint analysis of Neutral Hydrogen ($\rm {H\,\small {I}}$) Intensity Mapping observations with three galaxy samples: the Luminous Red Galaxy (LRG) and Emission Line Galaxy (ELG) samples from the eBOSS survey, and the WiggleZ Dark Energy Survey sample. The $\rm {H\,\small {I}}$ intensity maps are Green Bank Telescope observations of the redshifted $21\rm cm$ emission on $100 \, {\rm deg}^2$ covering the redshift range 0.6 < z < 1.0. We process the data by separating and removing the foregrounds present in the radio frequencies with FastI ICA. We verify the quality of the foreground separation with mock realizations, and construct a transfer function to correct for the effects of foreground removal on the $\rm {H\,\small {I}}$ signal. We cross-correlate the cleaned $\rm {H\,\small {I}}$ data with the galaxy samples and study the overall amplitude as well as the scale dependence of the power spectrum. We also qualitatively compare our findings with the predictions by a semianalytical galaxy evolution simulation. The cross-correlations constrain the quantity $\Omega _{\rm {H\,\small {I}}} b_{\rm {H\,\small {I}}} r_{\rm {H\,\small {I}},{\rm opt}}$ at an effective scale k eff , where $\Omega _\rm {H\,\small {I}}$ is the $\rm {H\,\small {I}}$ density fraction, $b_\rm {H\,\small {I}}$ is the $\rm {H\,\small {I}}$ bias, and $r_{\rm {H\,\small {I}},{\rm opt}}$ the galaxy–hydrogen correlation coefficient, which is dependent on the $\rm {H\,\small {I}}$ content of the optical galaxy sample. At $k_{\rm eff}=0.31 \, h\,{\rm Mpc^{-1}}$ we find $\Omega _{\rm {H\,\small {I}}} b_{\rm {H\,\small {I}}} r_{\rm {H\,\small {I}},{\rm Wig}} = [0.58 \pm 0.09 \, {\rm (stat) \pm 0.05 \, {\rm (sys)}}] \times 10^{-3}$ for GBT-WiggleZ, $\Omega _{\rm {H\,\small {I}}} b_{\rm {H\,\small {I}}} r_{\rm {H\,\small {I}},{\rm ELG}} = [0.40 \pm 0.09 \, {\rm (stat) \pm 0.04 \, {\rm (sys)}}] \times 10^{-3}$ for GBT-ELG, and $\Omega _{\rm {H\,\small {I}}} b_{\rm {H\,\small {I}}} r_{\rm {H\,\small {I}},{\rm LRG}} = [0.35 \pm 0.08 \, {\rm (stat) \pm 0.03 \, {\rm (sys)}}] \times 10^{-3}$ for GBT-LRG, at z ≃ 0.8. We also report results at $k_{\rm eff}=0.24$ and $k_{\rm eff}=0.48 \, h\,{\rm Mpc^{-1}}$. With little information on $\rm {H\,\small {I}}$ parameters beyond our local Universe, these are amongst the most precise constraints on neutral hydrogen density fluctuations in an underexplored redshift range.

79 ASTRONOMY AND ASTROPHYSICS↗

Ab initio phonon dispersion in crystalline naphthalene using van der Waals density functionals

Acene molecular crystals are of current interest in organic optoelectronics, both as active materials and for exploring and understanding new phenomena. Phonon scattering can be an important facilitator and dissipation mechanism in charge separation and carrier transport processes. Here, we carry out density functional theory (DFT) calculations of the structure and the full phonon dispersion of crystalline naphthalene, a well-characterized acene crystal for which detailed neutron-diffraction measurements, as well as infrared and Raman spectroscopy, are available. We evaluate the performance, relative to experiments, of DFT within the local density approximation (LDA); the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE); and a recent van der Waals-corrected nonlocal correlation (vdW-DF-cx) functional. We find that the vdW-DF-cx functional accurately predicts lattice parameters of naphthalene within 1%. Intermolecular and intramolecular phonon frequencies across the Brillouin zone are reproduced within 7.8% and 1%, respectively. As expected, LDA (PBE) underestimates (overestimates) the lattice parameters and overestimates (underestimates) phonon frequencies, demonstrating their shortcomings for predictive calculations of weakly bound materials. If the unit cell is fixed to the experimental lattice parameters, PBE is shown to lead to improved phonon frequencies. Our study provides a detailed understanding of the phonon spectrum of naphthalene, and highlights the importance of including van der Waals dispersion interactions in predictive calculations of lattice parameters and phonon frequencies of molecular crystals and related organic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗