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The trends in reactivity of CF(n) radicals with SiO2 and the site selectivity of the attack are studied using two different cluster models. The reaction barriers for the most energetically favorable reaction are computed. It is shown that CF(n) radicals are fairly unreactive towards SiO2.
The multi-principal element alloy nanoparticles (MPEA NPs), a new class of nanomaterials, present a highly rewarding opportunity to explore new or vastly different functional properties than the traditional mono/bi/multimetallic nanostructures due to their unique characteristics of atomic-level homogeneous mixing of constituent elements in the nanoconfinements. Here, in this paper, the successful creation of NiCoCr nanoparticles, a well-known MPEA system is reported, using ultrafast nanosecond laser-induced dewetting of alloy thin films. Nanoparticle formation occurs by spontaneously breaking the energetically unstable thin films in a melt state under laser-induced hydrodynamic instability and subsequently accumulating in a droplet shape via surface energy minimization. While NiCoCr alloy shows a stark contrast in physical properties compared to individual metallic constituents, i.e., Ni, Co, and Cr, yet the transient nature of the laser-driven process facilitates a homogeneous distribution of the constituents (Ni, Co, and Cr) in the nanoparticles. Using high-resolution chemical analysis and scanning nanodiffraction, the environmental stability and grain arrangement in the nanoparticles are further investigated. Thermal transport simulations reveal that the ultrashort (≈100 ns) melt-state lifetime of NiCoCr during the dewetting event helps retain the constituent elements in a single-phase solid solution with homogenous distribution and opens the pathway to create the unique MPEA nanoparticles with laser-induced dewetting process.
Five novel tetravalent thorium (Th) compounds that consist of Th(H 2 O) x Cl y structural units were isolated from acidic aqueous solutions using a series of nitrogen-containing heterocyclic hydrogen (H) bond donors. Taken together with three previously reported phases, the compounds provide a series of monomeric Th IV complexes wherein the effects of noncovalent interactions (and H-bond donor identity) on Th structural chemistry can be examined. Seven distinct structural units of the general formulas [Th(H 2 O) x Cl 8–x ] x-4 (x = 2, 4) and [Th(H 2 O) x Cl 9–x] x-5 (x = 5–7) are described. The complexes range from chloride-deficient [Th(H 2 O) 7 Cl 2 ] 2+ to chloride-rich [Th(H 2 O) 2 Cl 6 ] 2– species, and theory was used to understand the relative energies that separate complexes within this series via the stepwise chloride addition to an aquated Th cation. Electronic structure theory predicted the reaction energies of chloride addition and release of water through a series of transformations, generally highlighting an energetic driving force for chloride complexation. To probe the role of the counterion in the stabilization of these complexes, electrostatic potential (ESP) surfaces were calculated. Finally, the ESP surfaces indicated a dependence of the chloride distribution about the Th metal center on the pK a of the countercation, highlighting the directing effects of noncovalent interactions (e.g., Hbonding) on Th speciation.
Monitoring of the Sun and the Earth has yielded new knowledge essential to this debate. There is now no doubt that the total radiative energy from the Sun that heats the Earth's surface changes over decadal time scales as a consequence of solar activity. Observations indicate as well that changes in ultraviolet radiation and energetic particles from the Sun, also connected with the solar activity, modulate the layer of ozone that protects the biosphere from the solar ultraviolet radiation. This report reassesses solar influences on global change in the light of this new knowledge of solar and atmospheric variability. Moreover, the report considers climate change to be encompassed within the broader concept of global change; thus the biosphere is recognized to be part of a larger, coupled Earth system. Implementing a program to continuously monitor solar irradiance over the next several decades will provide the opportunity to estimate solar influences on global change, assuming continued maintenance of observations of climate and other potential forcing mechanisms. In the lower atmosphere, an increase in solar radiation is expected to cause global warming. In the stratosphere, however, the two effects produce temperature changes of opposite sign. A monitoring program that would augment long term observations of tropospheric parameters with similar observations of stratospheric parameters could separate these diverse climate perturbations and perhaps isolate a greenhouse footprint of climate change. Monitoring global change in the troposphere is a key element of all facets of the United States Global Change Research Program (USGCRP), not just of the study of solar influences on global change. The need for monitoring the stratosphere is also important for global change research in its own right because of the stratospheric ozone layer.
The energy budget of the tropical western Pacific (TWP) is particularly important because this is one of the most energetic convection regions on the Earth. Nearly half of the solar radiation incident at the top of atmosphere is absorbed at the surface and only about 22% absorbed in the atmosphere. A large portion of the excess heat absorbed at the surface is transferred to the atmosphere through evaporation, which provides energy and water for convection and precipitation. The western equatorial Pacific is characterized by the highest sea surface temperature (SST) and heaviest rainfall in the world ocean. A small variation of SST associated with the eastward shift of the warm pool during El-Nino/Souther Oscillation changes the atmospheric circulation pattern and affects the global climate. In a study of the TWP surface heat and momentum fluxes during the Tropical Ocean and Global Atmosphere Coupled Ocean-Atmosphere Response Experiment (TOGA COARE) Intensive observing period (IOP) from November 1992 to February have found that the solar radiation is the most important component of the surface energy budget, which undergoes significant temporal and spatial variation. The variations are influenced by the two 40-50 days Madden Julian Oscillations (MJOs) which propagated eastward from the Indian Ocean to the Central Pacific during the IOP. The TWP surface solar radiation during the COARE IOP was investigated by a number of studies. In addition, the effects of clouds on the solar heating of the atmosphere in the TWP was studied using energy budget analysis. In this study, we present some results of the TWP surface solar shortwave or SW radiation budget and the effect of clouds on the atmospheric solar heating using the surface radiation measurements and Japan's Geostationary Meteorological Satellite 4 radiance measurements during COARE IOP.
Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.
Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. there is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.
Thermodynamic calculations showed that the autotrophic synthesis of all 20 protein-forming amino acids was energetically favored in hot (100 degrees C), moderately reduced, submarine hydrothermal solutions relative to the synthesis in cold (18 degrees C), oxidized, surface seawater. The net synthesis reactions of 11 amino acids were exergonic in the hydrothermal solution, but all were endergonic in surface seawater. The synthesis of the requisite amino acids of nine thermophilic and hyperthermophilic proteins in a 100 degreesC hydrothermal solution yielded between 600 and 8000 kilojoules per mole of protein, which is energy that is available to drive the intracellular synthesis of enzymes and other biopolymers in hyperthermophiles thriving in these ecosystems.
Terahertz (THz) spectroscopy provides a noncontact method to measure the ultrafast dynamics and photoconductivity of mobile carriers in semiconducting materials. This has proven useful in studying artificial photosynthesis devices which use semiconductor photoelectrodes. In this work, we present a brief introduction to optical-pump THz-probe (OPTP) spectroscopy, a technique that provides unique and useful insight into interfacial electron transfer (from the surface-attached dye to the conduction band of the semiconductor) in dye-sensitized photoelectrochemical cells. Compared with more familiar methods like visible transient absorption spectroscopy, OPTP spectroscopy stands out in offering both sub-picosecond time resolution as well as sensitivity to mobile carriers (electrons and holes) in the semiconductor portion of artificial photosynthesis devices. The mobile carriers are crucial to device performance as only they pass to the other half cell to complete the reaction. In order to highlight these advantages and illustrate the types of questions OPTP spectroscopy can address, we discuss three case studies. In the first, OPTP spectroscopy is used to measure the injection rates from a set of six different dyes, revealing the effect of the energetics and lifetimes of the dye excited states on interfacial electron transfer. The subsequent case studies investigate the influence of varying the moieties which bind to the surface (anchors), as well as the moieties that connect the chromophore with these anchors (linkers). OPTP spectroscopy was used to measure the interfacial electron transfer rate as these moieties were varied.
The penetration depth of low-energy heavy ions in botanic samples was detected with a new transmission measurement. In the measurement, highly oriented pyrolytic graphite (HOPG) pieces were placed behind the botanic samples with certain thickness. During the irradiation of heavy ions with energy of tens of keV, the energetic particles transmitted from those samples were received by the HOPG pieces. After irradiation, scanning tunneling microscope (STM) was applied to observe protrusion-like damage induced by these transmitted ions on the surface of the HOPG. The statistical average number density of protrusions and the minimum transmission rate of the low-energy heavy ions can be obtained. The detection efficiency of the new method for low-energy heavy ions was about 0.1-1 and the background in the measurement can be reduced to as low as 1.0 x 10(8) protrusions/cm2. With this method, the penetration depth of the energetic particles was detected to be no less than 60 micrometers in kidney bean slices when the slices were irradiated by 100 keVAr+ ion at the fluence of 5 x 10(16) ions/cm2. c2002 Elsevier Science Ltd. All rights reserved.
The ion engine operations on Applied Technology Satellite 6 (ATS-6) altered the charge state of the spacecraft, changing the spacecraft surface potentials with respect to the distant plasmas. Plasma emission in quiet environments (plasma temperatures below 1 keV) caused the spacecraft potential to shift from a few volts positive to a few volts negative. A net ion current is emitted in such cases. The emission of a plasma or beam in energetic environments (plasma temperatures in the 5-10-keV range) in sunlight caused larger changes. Typical equilibrium potentials for ATS-6 in such environments were on the order of a hundred volts negative, with variations in potential across the spacecraft surface of comparable magnitude. Engine operations under such conditions raised the mainframe potential to near zero volts, and discharged the differential potentials on the dielectric surfaces. Plasma emission by the plasma bridge was an effective method of discharging kilovolt potentials in eclipse.
SelenITA is a dual CubeSat mission that will provide the first multi-point dust, plasma, and magnetic field measurements in lunar orbit. This mission will advance the understanding of the electromagnetic space environment at the Moon in support of the Artemis program, exploration, and the geosciences. Here we present the science rationale motivating the mission. The candidate mission science objectives include: (1) constrain the origins of crustal magnetic fields; (2) determine the nature of plasma interactions with crustal magnetic fields; (3) characterize plasma waves and turbulence at the Moon; (4) characterize the lunar surface electric potential in varying plasma environments; (5) constrain the composition, thermal state, and structure of the lunar upper mantle and crust; (6) characterize the ionizing radiation in lunar orbit; and lastly, (7) determine the density of the dust exosphere as a function of latitude, longitude, and altitude, including the lunar polar space environment. The measurement requirements include simultaneous two-point observations of the 3-component vector magnetic field, plasma distribution (flux, energy, density, temperature), and single-point observations of energetic particles (protons, electrons, gamma rays), and dust. These measurements are important because it helps us understand how future astronauts, robots, and space hardware will live and work on the lunar surface.
SelenITA is a dual CubeSat mission that will provide the first multi-point dust, plasma, and magnetic field measurements in lunar orbit. This mission will advance the understanding of the electromagnetic space environment at the Moon in support of the Artemis program, exploration, and the geosciences. Here we present the science rationale motivating the mission. The candidate mission science objectives include: (1) constrain the origins of crustal magnetic fields; (2) determine the nature of plasma interactions with crustal magnetic fields; (3) characterize plasma waves and turbulence at the Moon; (4) characterize the lunar surface electric potential in varying plasma environments; (5) constrain the composition, thermal state, and structure of the lunar upper mantle and crust; (6) characterize the ionizing radiation in lunar orbit; and lastly, (7) determine the density of the dust exosphere as a function of latitude, longitude, and altitude, including the lunar polar space environment. The measurement requirements include simultaneous two-point observations of the 3-component vector magnetic field, plasma distribution (flux, energy, density, temperature), and single-point observations of energetic particles (protons, electrons, gamma rays), and dust. These measurements are important because it helps us understand how future astronauts, robots, and space hardware will live and work on the lunar surface.
Understanding the structure–property relationships in layered transition-metal carbides or nitrides, known as MXenes, is of critical importance for their rational design, synthesis, and application. However, the vast chemical and structural diversity of MXenes, stemming from their wide range of M and X elements, surface terminations, and different atomic coordination environments, makes it challenging to clearly understand these structure–property relationships. Here, in this work, we perform first-principles density functional theory (DFT) calculations and molecular dynamics (MD) simulations to comprehensively investigate the stability and a variety of physical properties of MXenes with different coordination environments. Using Ti- and Mo-based carbide MXenes as model systems, energetic calculations reveal that Ti-based MXenes are most stable in octahedral coordination, whereas Mo-based MXenes preferentially adopt prismatic coordination. This fundamental difference in preferred atomic coordination gives rise to markedly distinct properties between these two systems as a function of the fraction of octahedral and prismatic sites. For instance, the in-plane stiffness of Ti-based MXenes increases as octahedral coordination becomes dominant, but it decreases in the Mo-based MXenes under the same conditions. Additional stability analyses based on mechanical, lattice-dynamical, and temperature-dependent thermodynamic properties demonstrate that many metastable MXenes not only satisfy the strict stability criteria but can also undergo phase transitions among different structures and even become stabilized at elevated temperatures. Although surface terminations, such as F and O atoms, do not alter the energetic ordering or the overall stiffness trends among stable and metastable MXenes, they influence other material properties. For instance, O termination can induce semiconducting behavior in both stable and metastable Ti 2 CO 2 MXenes. This study significantly advances the fundamental understanding of structure–property relationships in MXenes and provides valuable guidance for developing coordination-based design principles to precisely engineer MXenes with improved properties.
Multi-principal component transition metal (TM) diborides represent a class of high-entropy ceramics (HECs) that have received considerable interest in recent years owing to their promising properties for extreme environment applications that include thermal/ environmental barriers, hypersonic vehicles, turbine engines, and next-generation nuclear reactors. While the addition of chemical disorder through the random distribution of TM elements on the cation sublattice has offered opportunities to tailor elastic stiffness and hardness, the effects of irradiation-induced structural damage on the physical properties of these complex materials have remained largely unexplored. To this end, changes in the hardness and elastic moduli of a high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 and three of its quaternary subsets following irradiation with 10 MeV gold (Au) ions to fluences of up to 6 × 10 15 Au cm -2 are investigated at the micrometer and sub-micrometer length-scales via the dispersion of laser-generated surface acoustic waves (SAW) and nanoindentation, respectively. The nanoindentation measurements show that the TM diborides exhibit an initial increase in hardness following irradiation with energetic Au ions, with a subsequent decrease in hardness following further irradiation. One quaternary composition, (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 , exhibits a notable exception to the trend and continues to exhibit an increase in hardness with ion irradiation fluence. Although differences in the absolute values of the effective elastic moduli obtained from the measured SAW dispersion and nanoindentation are observed (and attributed to microstructural variations at the measurement length-scale), both techniques yield similar trends in the form of an initial reduction and subsequent saturation in the elastic modulus with increasing ion irradiation fluence. The quaternary TM diboride (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 again exhibits a departure from this trend. The high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 exhibits the greatest recovery in hardness and modulus when irradiated to high ion fluences following initial changes at low fluence, indicating superior resistance to radiation-induced damage over its quaternary counterparts. Opportunities for designing HECs with superior hardness and modulus for enhanced radiation resistance (compared to their single constituent counterparts) by tailoring chemical disorder and bond character in the lattice are discussed.
The Space Shuttle flights provided the first significant data base on the environment experienced by a large space structure operating in LEO. A number of interesting and unanticipated effects were observed, including material erosion induced by ambient oxygen atoms, the visible Shuttle glow occurring above surfaces exposed to the ram flow, and large near-field perturbations and variability in the gaseous neutral and plasma environment about the Shuttle. This paper provides a brief overview of these observations and their phenomenological interpretation, and then discusses laboratory approaches to their investigation. The emphasis is on the state of the art in the development of energetic oxygen atoms sources and the variety of experiments presently being performed with such devices.
We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.
A selected set of optically transparent specimens and first surface mirror specimens have been examined subsequent to on-orbit exposure. Certain specimens were from the Passive Optical Sample Assembly I and II experiments flown on the MIR Space Station. Other specimens were from the Energetic Oxygen Interaction with materials III experiment flown on the STS in August 1992. A comparison of pre- and post-flight transmission of reflectance measurements, as appropriate, has been carried out. Data from different specimens includes results of measurements for IR, optical, UV and/or vacuum UV wavelength intervals. Results of these measurements clearly show the effects of molecular contamination deposits on the surfaces during the on-orbit exposures. Surface analysis on a attracted set of specimens provides and estimate of contaminant thickness and composition and provides an insight into on-orbit deposition rates and surface oxidation reactions. For both the EOIM III and POSA I & II experiments, the primary source of contamination were outgassed silicones. Both experiments received approximately the same fluence of atomic oxygen (approx. 1-2 x 1020 atoms per square centimeter). ROSA specimens received between approx. 400 and 580 equivalent sun hours (ESH) of solar radiation over an 18 month period in orbit. The EOIM specimens were on an STS flight of about 1 week duration and received only approx. 5-10 ESH of solar radiation.