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Utilizing a crossed electron beam-molecular beam collision geometry, mass spectra of C(sub 60) and C(sub 70) ions have been obtained for an electron impact energy range of 20 eV to 600 eV.
The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.
We have constructed three-dimensional models for the equilibrium abundance of molecular hydrogen in diffuse interstellar clouds of arbitrary geometry that are illuminated by ultraviolet radiation. The position-dependent photodissociation rate of H2 in such clouds was computed with a 26 ray approximation to model the attenuation of the incident ultraviolet radiation field by dust and by H2 line absorption. We have applied our modeling technique to the isolated diffuse cloud G236+39, assuming that the cloud has a constant density and that the thickness of the cloud along the line of sight is at every point proportional to the 100 micron continuum intensity measured by IRAS. We find that our model can successfully account for observed variations in the ratio of 100 micron continuum intensity to H I column density, with larger values of that ratio occurring along lines of sight in which the molecular hydrogen fraction is expected to be the largest. Using a standard chi square analysis to assess the goodness of fit of our models, we find (at the 60 a level) that a three-dimensional model is more successful in matching the observational data than a one-dimensional model in which the geometrical extent of the cloud along the line of sight is assumed to be much smaller than its extent in the plane of the sky. If D is the distance to G236 + 39, and given standard assumptions about the rate of grain-catalyzed H2 formation, we find that the cloud has an extent along the line of sight that is 0.9 +/- 0.1 times its mean extent projected onto the plane of the sky and a gas density of 53 +/- 8 (100 pc/D) H nuclei/cc and is illuminated by a radiation field of 1.1 +/- 0.2 (100 pc/D) times the mean interstellar radiation field. The derived 100 micron emissivity per nucleon is 1.13 +/- 0.06 x 10(exp -20) MJy/sr sq cm.
Background: Molecular diagnostics provide early and accurate diagnosis, which is essential for the prevention and treatment of infectious as well as chronic diseases. These tests are designed to detect disease-specific bioanalytes such as nucleic acid (DNA or RNA) or protein (antigens, antibodies) biomarkers. In the context of infectious disease diagnosis, nucleic acid-based detection methods are known to provide more specific and sensitive results. Here, the presence of a unique sequence belonging to the pathogenic genomic material is targeted to identify species, organism, genera and/or antimicrobial resistant gene markers. The majority of the common nucleic acid based diagnostic techniques require amplification (polymerase chain reaction, isothermal amplification etc.) of the pathogenic genetic material prior to detection impacting diagnostic speed, complexity, and cost thereby limiting ease of use. Thus, the development of simplified nucleic acid-based diagnostics that can be even used in resource-poor settings may hugely benefit patients across the globe. Nanopath is a molecular diagnostics company utilizing a solid-state nanosensor to enable sequence-specific detection of target nucleic acids without the need of amplification. These nanostructures enable ultra-sensitive biomarker detection using geometric, feature-dependent properties highly dependent on the local dielectric environment, allowing them to be sensitive to low concentration binding events. This paper describes an application of this approach to provide highly relevant clinical information within a single doctor’s office visit. Intro: The Nanopath team is in collaboration with NASA (National Aeronautics and Space Administration) and NIST (National Institute of Standards and Technology) to push the bounds of the fundamental physics associated with their biosensing platform. The ability of metals to support electromagnetic surface waves gives rise to surface plasmons when optically illuminated. This property, and its strong sensitivity to changes in the local refractive index, allows for the use of metal nanoparticles as ultra-sensitive transducers. In prior work by members of this team, ensembles of randomly oriented nanoparticles (i.e., colloidal nanorods dispersed on chip) were employed for sequence-specific nucleic acid sensing (1-3). While these particle sensors have the advantage of rapid fabrication, they suffer from low sensitivity and quality factor due to the random particle dispersity. In contrast, in this study we employ ordered array nanoparticle ensembles which can be used to improve sensor sensitivity and figure-of-merit. Study Methods Overview: In this talk, we detail the results of sensing experiments and computational simulations to outline a rational design of the structure of these plasmonic nanoparticle arrays for biomolecular sensing. Through simulation and experiment, we iteratively tailor nanostructure dimension to provide high quality signal and large resonance shifts upon modeled nucleic acid binding. In particular, full-wave electromagnetic simulations were conducted using Lumerical photonic simulation software in which periodic boundary conditions were applied in the x- and y- dimensions for each of the nanoplasmonic sensor geometries. To simulate the resonance response to changes in the bulk solution in contact with the sensor surface, the refractive index of the surrounding media was changed appropriately. Nucleic acid hybridization events were modeled using either using spherical structures approximating the relevant radius of genomic material as estimated by polymer models, or as conformal layers with the known refractive indices for nucleic acids. On the basis of initial simulations, nanosensors were fabricated using traditional electron-beam lithography protocols at NIST. To evaluate consensus between simulations and experiments, bulk sensing experiments were carried out in which the resonance peaks were obtained by submerging the sensors in refractive index standards. Key nanosensor characteristics including resonance peak locations, resonance peak shifts as a function of refractive index, and figure of merit (FOM) of extinction curves were examined between the experimental and simulation results prior to proceeding with simulations on additional geometries and more complex solution conditions, and further device fabrication. This iterative process is repeated toward a rational design of nanoplasmonic array geometries for biosensing optimizing response for targeted disease detection. In summary, this study puts forth a methodology for rational design and characterization of regularly spaced nanoparticle arrays for optics-based biosensing. The results of this study will allow for more informed design of nanostructure geometries towards sequence-specific nucleic acid detection. These improved designs have the potential to improve clinical sensitivity and limit-of-detection across disease indication.
Multimodal chromatography is a powerful approach for purifying proteins that uses ligands containing multiple modes of interaction. Recent studies have shown that selectivity in multimodal chromatographic separations is a function of the ligand structure and geometry. Here, we performed molecular dynamics simulations to explore how the ligand structure and geometry affect ligand–water interactions and how these differences in solution affect the nature of protein–ligand interactions. Our investigation focused on three chromatography ligands: Capto MMC, Nuvia cPrime, and Prototype 4, a structural variant of Nuvia cPrime. First, the solvation characteristics of each ligand were quantified via three metrics: average water density, fluctuations, and residence time. We then explored how solvation was perturbed when the ligand was bound to the protein surface and found that the probability of the phenyl ring dewetting followed the order: Capto MMC > Prototype 4 > Nuvia cPrime. To explore how these differences in dewetting affect protein–ligand interactions, we calculated the probability of each ligand binding to different types of residues on the protein surface and found that the probability of binding to a hydrophobic residue followed the same order as the dewetting behavior. This study illustrates the role that wetting and dewetting play in modulating protein–ligand interactions.
Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads—one-dimensional diamondoid polymers formed through the compression of small molecules—represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid. The resulting product possesses high-density, pendant carboxyl functionalization along both sides of the backbone, enabling new opportunities for the post-synthetic processing and chemical modification of nanothread materials applicable to a broad range of potential applications.
Abstract Organic photovoltaics (OPV) are one of the most effective ways to harvest renewable solar energy, with the power conversion efficiency (PCE) of the devices soaring above 19 % when processed with halogenated solvents. The superior photocurrent of OPV over other emerging photovoltaics offers more opportunities to further improve the efficiency. Tailoring the absorption band of photoactive materials is an effective way to further enhance OPV photocurrent. However, the field has mostly been focusing on improving the near‐infrared region photo‐response, with the absorption shoulders in short‐wavelength region (SWR) usually being neglected. Herein, by developing a series of non‐fullerene acceptors (NFAs) with varied side‐group conjugations, we observe an enhanced SWR absorption band with increased side‐group conjugation length. The underpinning factors of how molecular structures and geometries improve SWR absorption are clearly elucidated through theoretical modelling and crystallography. Moreover, a clear relationship between the enhanced SWR absorption and reduced singlet‐triplet energy gap is established, both of which are favorable for the OPV performance and can be tailored by rational structure design of NFAs. Finally, the rationally designed NFA, BO‐TTBr, affords a decent PCE of 18.5 % when processed with a non‐halogenated green solvent.
The construction of multinuclear lanthanide-based molecules with significant magnetic exchange interactions represents a key challenge in the realization of single-molecule magnets with high operating temperatures. Here, we report the synthesis and magnetic characterization of two series of heterobimetallic compounds, (Cp* 2 Ln) 2 (μ-Co(pdt) 2 ) (Ln = Y 3+ , Gd 3+ , Dy 3+ ; pdt 2– = 1,2-diphenylethylenedithiolate) and [K(18-crown-6)][(Cp* 2 Ln) 2 (μ-Co(pdt) 2 )] (Ln = Y 3+ , Gd 3+ ), featuring two lanthanide centers bridged by a cobalt bis(1,2-dithiolene) complex. Dc magnetic susceptibility data collected for the Gd congeners indicate significant Gd–Co ferromagnetic exchange interactions with fits affording J = +11.5 and +7.33 cm –1 , respectively. Magnetization decay and ac magnetic susceptibility measurements carried out on the single-molecule magnet (Cp* 2 Dy) 2 (μ-Co(pdt) 2 ) reveal full suppression of quantum tunneling and open-loop hysteresis persisting up to 3.5 K. These results, along with those of high-field EPR spectroscopy, suggest that transition metalloligands can enforce strong exchange interactions with adjacent lanthanide centers while maintaining a geometry that preserves molecular anisotropy. Furthermore, the magnetic properties of [K(18-crown-6)][(Cp* 2 Gd) 2 (μ-Co(pdt) 2 )] show that increasing the spin of the ground state of the bridging complex may be a viable alternative to increasing J in obtaining well-isolated, strongly coupled magnetic ground states.
The Hellmann–Feynman (HF) theorem provides a way to compute forces directly from the electron density, enabling efficient force calculations for large systems through machine learning (ML) models for the electron density. The main issue holding back the general acceptance of the HF approach for atom-centered basis sets is the well-known Pulay force which, if naively discarded, typically constitutes an error upward of 10 eV/Å in forces. In this work, we demonstrate that if a suitably augmented Gaussian basis set is used for density functional calculations, the Pulay force can be suppressed, and HF forces can be computed as accurately as analytical forces with state-of-the-art basis sets, allowing geometry optimization and molecular dynamics to be reliably performed with HF forces. Our results pave a clear path forward for the accurate and efficient simulation of large systems using ML densities and the HF theorem.
Using a crossed electron beam-molecular beam scattering geometry and a relative-flow technique, ratios of elastic differential cross sections of CO to those of He have been measured at electron impact energies of 3, 5, 7.5, 9.9, 15, 20, 30, 50, 75, and 100 eV. At each energy, an angular range of 15 to 130 deg has been covered. These ratios have been multiplied by previously known He elastic differential cross sections to obtain elastic differential cross sections for CO. Since pure rotational excitations were not resolved, the elastic differential cross sections are a sum of elastic and pure rotational excitations at room temperature. From a knowledge of differential cross sections (DCS), integral and momentum transfer cross sections have been calculated. Both the DCS and integral cross sections are compared at 50, 75, and 100 eV to a recent two-potential theory of e-molecule scattering. Present results show that the isoelectronic molecules CO and N2 have very similar magnitudes and shapes of their differential cross sections.
Utilizing a crossed electron-beam-molecular-beam scattering geometry, relative values of differential electron scattering cross sections for cesium chloride at 5 and 20 eV electron impact energies and at scattering angles between 10 and 120 deg have been measured. These relative cross sections have been normalized to the cross section at 15 deg scattering angle calculated by the hybrid S-matrix technique. In the angular range between 0 and 10 deg and between 120 and 180 deg extrapolations have been made to obtain integral and momentum transfer cross sections. An energy-loss spectrum is also presented which gives various spectral features lying between the 4 and 10 eV regions in CsCl.
A crossed electron beam-molecular beam scattering geometry and the relative-flow technique are used to measure the ratios of the elastic differential cross sections of SO2 to those of He at electron impact energies of 12, 20, 50, 100, 150, and 200 eV. At each energy, an angular range of 15-150 deg is covered. The ratios are multiplied by previously known He elastic differential cross sections to obtain elastic differential cross sections for SO2. Integral and momentum transfer cross sections are then determined from a knowledge of differential cross sections. With the aid of the two-potential theory of e-molecule scattering, calculations are also performed and compared with the measurements.
A crossed electron beam-molecular beam collision geometry is used to measure cross sections for the production of positive ions by electron impact on NH3 and CS2. Ionization cross-section data for NH3 and the values of various cross sections are presented, as well as ionization efficiency curves for CS2. Considerable differences are found between the various results on NH3. The present values are close to the data of Djuric et al. (1981). The semiempirical calculations of Hare and Meath (1987) differ considerably in the absolute values of cross sections. Discrepancies were observed in comparisons of cross sections of other fragment ions resulting from the ionization and dissociate ionization of NH3.
Using a crossed electron beam-molecular beam collision geometry and the relative flow technique measurements have been made to generate a uniform set of electron impact ionization cross-section data for O2 for electron impact energies from threshold to 1000 eV. Present values of total, partial and dissociative ionization cross-sections are compared with previously published data. Cross-sections for the formation of O2(+) from O2 have been measured for the first time.
An experimental investigation of the non-reactive mixing processes associated with a lobed fuel injector in a coflowing air stream is presented. The lobed fuel injector is a device which generates streamwise vorticity, producing high strain rates which can enhance the mixing of reactants while delaying ignition in a controlled manner. The lobed injectors examined in the present study consist of two corrugated plates between which a fuel surrogate, CO2, is injected into coflowing air. Acetone is seeded in the CO2 supply as a fuel marker. Comparison of two alternative lobed injector geometries is made with a straight fuel injector to determine net differences in mixing and strain fields due to streamwise vorticity generation. Planar laser-induced fluorescence (PLIF) of the seeded acetone yields two-dimensional images of the scalar concentration field at various downstream locations, from which local mixing and scalar dissipation rates are computed. It is found that the lobed injector geometry can enhance molecular mixing and create a highly strained flowfield, and that the strain rates generated by scalar energy dissipation can potentially delay ignition in a reacting flowfield.
Single crystal X-ray diffraction analysis is one of the more important methods for the molecular and crystal structure determination of matter and therefore it has a great importance in material science including design and engineering of different compounds with non-linear optical (NLO) properties. It was shown in our previous publications that this method provides unique information about molecular structure of NLO compounds, their crystal symmetry and crystal packing arrays, molecular conformation and geometries and many other structural and electronic characteristics that are important for understanding the nature of NLO properties of solids. A very new application of the X-ray diffraction method is related to analysis of the electron density distribution p(r) in crystals and some of its characteristics (atomic and group charges, dipole and higher multipole moments, etc.), that may be obtained directly form the diffraction measurements. In the present work, we will discuss our preliminary low temperature high-resolution X-ray data for the m-nitroaniline (mNA) single crystal (VI). This is one of the "classical" organic NLO materials and electron density distribution analysis in this simple compound has a great scientific interest.
Water is present in the atmospheres of 6 of the 9 planets. Cross section values for the direct and partial ionization of H2O by electron impact have been measured and compared with previously published data. The present measurements have been carried out from thresholds to 1 KeV by utilizing a crossed electron beam and molecular beam collision geometry and an improved ion extraction technique.