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The interplay of covalency, hydrogen bonding, and dispersion leads to a long range chiral network: The example of 2-butanol
The assembly of complex structures in nature is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Understanding and ultimately controlling the self-assembly of materials requires extensive study of how these forces drive local nanoscale interactions and how larger structures evolve. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol has recently been shown to have interesting properties as a chiral modifier of surface chemistry; however, its mode of action is not fully understood and a microscopic understanding of the role non-covalent interactions play in its adsorption and assembly on surfaces is lacking. In order to probe its surface properties, we employed high-resolution scanning tunneling microscopy and density functional theory (DFT) simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule’s intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations, however, reveal that the tetramers are stable entities that are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. This network of homochiral square pores grows to cover the whole Au(111) surface. Our data reveal that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen-bonded networks and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network’s enantioselective interaction with other molecules.
Optical heterodyne-enhanced chirped laser dispersion spectroscopy
A proof-of-concept heterodyne-enhanced chirped laser dispersion spectroscopy system is presented. In remote sensing systems where low return powers are expected, the addition of an optical local oscillator and subsequent nonlinear processing can provide improved performance in chirped laser dispersion spectroscopy. Here, details about the system configuration, phase noise cancellation, and experimental verification are discussed.
Dual;#8208;Metal Interbonding as the Chemical Facilitator for Single;#8208;Atom Dispersions
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Mechanistic insight into the passive NOx adsorption in the highly dispersed Pd/HBEA zeolite
Passive NOx adsorption using zeolite supported Pd catalysts has been considered one of most effective methods for low-temperature NO storage in diesel engine emission control. In the present work, first-principles density functional theory calculations were used to study NO adsorption at the highly dispersed Pd sites, i.e., monomeric PdIIO and dimeric [PdIIOPdII]2+ in the H-BEA zeolite. It has been found that each PdIIO and [PdIIOPdII]2+ sites could bind with three and four NO molecules, respectively. Upon adsorption, NO could be oxidized to NO2, resulting in the reduction of PdII to Pd0 for PdIIO and PdII to PdI, for [PdIIOPdII]2+, respectively. With increasing NO coverage at both sites, NO oxidation becomes more facile with low activation barriers of 13 and 22 kJ/mol. At the PdIIOPdII site, the binding of formed NO2 becomes weak at high NO coverage. Both PdIIO and [PdIIOPdII]2+ sites are protonated to the more stable [PdIIOH]+ and [PdIIOH]+/[PdIIOH]+ sites in the presence of H2O or neighboring BAS sites. Finally, we studied the CO effect on the NO adsorption in Pd/H-BEA. With co-fed CO in the NOx mixture, both PdIIO and [PdIIOPdII]2+ could be reduced to Pd0 and [PdI-PdI]2+ sites. Compared to the NO adsorption, our calculations show that CO adsorption is slightly stronger at the [PdIIOPdII]2+ site while it is slightly weaker at the PdIIO site. CO oxidation, rather than NO oxidation readily occurs if NO and CO co-adsorbed. The reduced PdI site and the [PdIIOH]+/[PdIIOH]+ site enhances NO adsorption.
Development of PRIME for irradiation performance analysis of U-Mo/Al dispersion fuel
Not Available
Measurement Error in Atomic-Scale Scanning Transmission Electron Microscopy—Energy-Dispersive X-Ray Spectroscopy (STEM-EDS) Mapping of a Model Oxide Interface
Abstract With the development of affordable aberration correctors, analytical scanning transmission electron microscopy (STEM) studies of complex interfaces can now be conducted at high spatial resolution at laboratories worldwide. Energy-dispersive X-ray spectroscopy (EDS) in particular has grown in popularity, as it enables elemental mapping over a wide range of ionization energies. However, the interpretation of atomically resolved data is greatly complicated by beam–sample interactions that are often overlooked by novice users. Here we describe the practical factors—namely, sample thickness and the choice of ionization edge—that affect the quantification of a model perovskite oxide interface. Our measurements of the same sample, in regions of different thickness, indicate that interface profiles can vary by as much as 2–5 unit cells, depending on the spectral feature. This finding is supported by multislice simulations, which reveal that on-axis maps of even perfectly abrupt interfaces exhibit significant delocalization. Quantification of thicker samples is further complicated by channeling to heavier sites across the interface, as well as an increased signal background. We show that extreme care must be taken to prepare samples to minimize channeling effects and argue that it may not be possible to extract atomically resolved information from many chemical maps.
Smooth Dispersion Is Physically Appropriate: Assessing and Amending the D4 Dispersion Model
The addition of dispersion corrections to density functionals is essential for accurate energy and geometry predictions. Among them, the D4 scheme is popular due to its low computational cost and high accuracy. However, due to its design, the D4 correction can occasionally lead to anomalies, such as unphysical curvature and bumps in the potential energy surface. We find these anomalies are common in the D4 model, although observable consequences are rarer than in the D3 model for reasons we explain. Nevertheless, we uncover instances of unphysical local minima and stationary points with the D4 scheme and propose two solutions that yield smoother dispersion energy as a function of nuclear position. One is trivial to implement, based on a smoother reparametrization of Gaussian weighting (D4S) to find the effective coordination number. The other replaces Gaussian weighting with soft linear interpolation (D4SL). These new approaches usually remove artificial extremum points, while maintaining accuracy.
Unveiling Active Sites of CO[subscript 2] Reduction on Nitrogen-Coordinated and Atomically Dispersed Iron and Cobalt Catalysts
Abstract not provided
Dispersive charge density wave excitations in Bi 2 Sr 2 CaCu 2 O 8+δ [Dispersive charge density wave excitations and temperature dependent commensuration in Bi 2 Sr 2 CaCu 2 O 8+δ ]
Experimental evidence on high-T c cuprates reveals ubiquitous charge density wave (CDW) modulations, which coexist with superconductivity. Although the CDW had been predicted by theory, important questions remain about the extent to which the CDW influences lattice and charge degrees of freedom and its characteristics as functions of doping and temperature. These questions are intimately connected to the origin of the CDW and its relation to the mysterious cuprate pseudogap. We use ultrahigh-resolution resonant inelastic X-ray scattering to reveal new CDW character in underdoped Bi 2.2 Sr 1.8 Ca 0.8 Dy 0.2 Cu 2 O 8+δ . At low temperature, we observe dispersive excitations from an incommensurate CDW that induces anomalously enhanced phonon intensity, unseen using other techniques. Furthermore, near the pseudogap temperature T*, the CDW persists, but the associated excitations significantly weaken with an indication of CDW wavevector shift. The dispersive CDW excitations, phonon anomaly, and analysis of the CDW wavevector provide a comprehensive momentum-space picture of complex CDW behaviour and point to a closer relationship with the pseudogap state.
Dispersal, habitat filtering, and eco-evolutionary dynamics as drivers of local and global wetland viral biogeography
Abstract Wetlands store 20–30% of the world’s soil carbon, and identifying the microbial controls on these carbon reserves is essential to predicting feedbacks to climate change. Although viral infections likely play important roles in wetland ecosystem dynamics, we lack a basic understanding of wetland viral ecology. Here 63 viral size-fraction metagenomes (viromes) and paired total metagenomes were generated from three time points in 2021 at seven fresh- and saltwater wetlands in the California Bodega Marine Reserve. We recovered 12,826 viral population genomic sequences (vOTUs), only 4.4% of which were detected at the same field site two years prior, indicating a small degree of population stability or recurrence. Viral communities differed most significantly among the seven wetland sites and were also structured by habitat (plant community composition and salinity). Read mapping to a new version of our reference database, PIGEONv2.0 (515,763 vOTUs), revealed 196 vOTUs present over large geographic distances, often reflecting shared habitat characteristics. Wetland vOTU microdiversity was significantly lower locally than globally and lower within than between time points, indicating greater divergence with increasing spatiotemporal distance. Viruses tended to have broad predicted host ranges via CRISPR spacer linkages to metagenome-assembled genomes, and increased SNP frequencies in CRISPR-targeted major tail protein genes suggest potential viral eco-evolutionary dynamics in response to both immune targeting and changes in host cell receptors involved in viral attachment. Together, these results highlight the importance of dispersal, environmental selection, and eco-evolutionary dynamics as drivers of local and global wetland viral biogeography.
Dispersion forces play a role in (Me 2 IPr)Fe(✓NAd)R 2 (Ad = adamantyl; R = neo Pe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)
Calculations show that dispersion forces in four-coordinate (Me 2 IPr)Fe(✓NAd)(1-nor) 2 ( 2b ) contribute to greater D(FeR) and subtly slow its migratory insertion relative to the neopentyl analogue.
Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers
Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles.
Hydrodynamic dispersion in thin channels with micro-structured porous walls
Flowand transport within porous- and microtextured-walled channels is relevant to a number of natural and industrial processes. Designing and optimizing the topology of the pores and/or microstructure to achieve target performance at the system scale (or macroscale) is still an open question. In this work, we study whether hydrodynamic dispersion in microfluidic channels with walls structured by obstacles can be modeled by dispersion in channels with porous walls described as continuous porous media of zero or finite permeability. We perform single phase microfluidic non-reactive flow experiments in channels embedded in micropatterns with different topologies. Specifically, we focus on transverse riblets and arrays of pillars as examples of impermeable and permeable obstructions, respectively. We compare the experimental results with three models: 3D pore-scale simulations which resolve the micropattern geometry explicitly and two upscaled models which treat the micropattern as a continuum of zero or finite permeability. This study demonstrates that polydimethylsiloxane micromodels with appropriately patterned surfaces can be successfully employed to validate various continuum-scale modeling approximations in different physical regimes, identified by the order of magnitude of the Peclet number and the obstruction permeability.
Dispersion-Based Fresh-Slice Scheme for Free-Electron Lasers
The fresh-slice technique improved the performance of several self-amplified spontaneous emission free-electron laser schemes by granting selective control on the temporal lasing slice without spoiling the other electron bunch slices. So far, the implementation has required a special insertion device to create the beam yaw, called a dechirper. Finally, we demonstrate a novel scheme to enable fresh-slice operation based on electron energy chirp and orbit dispersion that can be implemented at any free-electron laser facility without additional hardware.
Urban Dispersion Virtual Workshop: Designing the Next Generation Urban Dispersion Field Programs
The overarching objective of this workshop is to start the process of planning and implementing the “Next Generation of Urban Dispersion Studies”. We have organized this program to bring people interested in this complex problem together. We have representation from different disciplines, different agencies, and different academic institutions. The workshop is organized around several questions: • What are the needs of the emergency response community and how do we design models and experiments to address them? • What model improvements do the user communities need? • How do we design tracer release and sampling to address questions temporal (e.g., diurnal and seasonal variation) and spatial (e.g., land/urban/water gradients) for the broadest applicability? • What are the next-generation measurements needed to improve the data sets? • How do we implement the next generation urban dispersion experiments? The Virtual workshop format is exciting. We view this as an experiment which, if successful, will bring a large group of people together from the community to design the next generation urban experiments. We have many agencies participating: DOE-BER, DHS, FEMA, NNSA, NARAC, DTRA, NYPD, and NIST. The registration list includes over 40 people including participants from well beyond the US including Spain and Canada.
Support the Design of Improved IUE NEWSIPS High Dispersion Extraction Algorithms: Improved IUE High Dispersion Extraction Algorithms
The objective of this work was to support the design of improved IUE NEWSIPS high dispersion extraction algorithms. The purpose of this work was to evaluate use of the Linearized Image (LIHI) file versus the Re-Sampled Image (SIHI) file, evaluate various extraction, and design algorithms for evaluation of IUE High Dispersion spectra. It was concluded the use of the Re-Sampled Image (SIHI) file was acceptable. Since the Gaussian profile worked well for the core and the Lorentzian profile worked well for the wings, the Voigt profile was chosen for use in the extraction algorithm. It was found that the gamma and sigma parameters varied significantly across the detector, so gamma and sigma masks for the SWP detector were developed. Extraction code was written.