46 research outputs found
Orbital Interaction Mechanisms of Conductance Enhancement and Rectification by Dithiocarboxylate Anchoring Group
We study computationally the electron transport properties of
dithiocarboxylate terminated molecular junctions. Transport properties are
computed self-consistently within density functional theory and nonequilibrium
Green's functions formalism. A microscopic origin of the experimentally
observed current amplification by dithiocarboxylate anchoring groups is
established. For the 4,4'-biphenyl bis(dithiocarboxylate) junction, we find
that the interaction of the lowest unoccupied molecular orbital (LUMO) of the
dithiocarboxylate anchoring group with LUMO and highest occupied molecular
orbital (HOMO) of the biphenyl part results in bonding and antibonding
resonances in the transmission spectrum in the vicinity of the electrode Fermi
energy. A new microscopic mechanism of rectification is predicted based on the
electronic structure of asymmetrical anchoring groups. We show that the peaks
in the transmission spectra of 4'-thiolato-biphenyl-4-dithiocarboxylate
junction respond differently to the applied voltage. Depending upon the origin
of a transmission resonance in the orbital interaction picture, its energy can
be shifted along with the chemical potential of the electrode to which the
molecule is more strongly or more weakly coupled
Effect of dry or wet substrate deposition on the organic volume fraction of core–shell aerosol particles
Understanding the impact of sea spray aerosol (SSA) on the
climate and atmosphere requires quantitative knowledge of their chemical
composition and mixing states. Furthermore, single-particle measurements are
needed to accurately represent large particle-to-particle variability. To
quantify the mixing state, the organic volume fraction (OVF), defined as the
relative organic volume with respect to the total particle volume, is
measured after generating and collecting aerosol particles, often using
deposition impactors. In this process, the aerosol streams are either dried
or kept wet prior to impacting on solid substrates. However, the atmospheric
community has yet to establish how dry versus wet aerosol deposition
influences the impacted particle morphologies and mixing states. Here, we
apply complementary offline single-particle atomic force microscopy (AFM)
and bulk ensemble high-performance liquid chromatography (HPLC) techniques
to assess the effects of dry and wet deposition modes on the
substrate-deposited aerosol particles' mixing states. Glucose and NaCl
binary mixtures that form core–shell particle morphologies were studied as
model systems, and the mixing states were quantified by measuring the OVF of
individual particles using AFM and compared to the ensemble measured by
HPLC. Dry-deposited single-particle OVF data positively deviated from the
bulk HPLC data by up to 60 %, which was attributed to significant
spreading of the NaCl core upon impaction with the solid substrate. This led
to underestimation of the core volume. This problem was circumvented by (a)Â performing wet deposition and thus bypassing the effects of the solid core
spreading upon impaction and (b) performing a hydration–dehydration cycle on
dry-deposited particles to restructure the deformed NaCl core. Both
approaches produced single-particle OVF values that converge well with the
bulk and expected OVF values, validating the methodology. These findings
illustrate the importance of awareness in how conventional particle
deposition methods may significantly alter the impacted particle
morphologies and their mixing states.</p
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Chemical Speciation of Sulfur in Marine Cloud Droplets and Particles: Analysis of Individual Particles from Marine Boundary Layer over the California Current
Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a combination of complementary microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from air masses that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with characteristic ratios of nss-S/Na>0.10 and CH3SO3-/nss-SO42->0.6
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Particle formation from pulsed laser irradiation of soot aggregates studied with a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope.
We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes
Characterization of Aerosols Containing Zn, Pb, and Cl from an Industrial Region of Mexico City
Recent ice core measurements show lead concentrations increasing since 1970, suggesting new non automobile-related sources of Pb are becoming important worldwide (1). Developing a full understanding of the major sources of Pb and other metals is critical to controlling these emissions. During the March, 2006 MILAGRO campaign, single particle measurements in Mexico City revealed the frequent appearance of particles internally mixed with Zn, Pb, Cl, and P. Pb concentrations were as high as 1.14 μg/m3 in PM10 and 0.76 μg/m3 in PM2.5. Real time measurements were used to select time periods of interest to perform offline analysis to obtain detailed aerosol speciation. Many Zn-rich particles had needle-like structures and were found to be composed of ZnO and/or Zn(NO3)2·6H2O. The internally mixed Pb-Zn-Cl particles represented as much as 73% of the fine mode particles (by number) in the morning hours between 2-5 am. The Pb-Zn-Cl particles were primarily in the submicrometer size range and typically mixed with elemental carbon suggesting a combustion source. The unique single particle chemical associations measured in this study closely match signatures indicative of waste incineration. Our findings also show these industrial emissions play an important role in heterogeneous processing of NOy species. Primary emissions of metal and sodium chloride particles emitted by the same source underwent heterogeneous transformations into nitrate particles as soon as photochemical production of nitric acid began each day at ~7 am
K.: Correlations between optical, chemical and physical properties of biomass burn aerosols, Geophys
Abstract Aerosols generated from burning different plant fuels were characterized to determine relationships between chemical, optical and physical properties. Single scattering albedo (ω) and Angstrom absorption coefficients (α ap ) were measured using a photoacoustic technique combined with a reciprocal nephelometer. Carbon-to-oxygen atomic ratios, sp 2 hybridization, elemental composition and morphology of individual particles were measured using scanning transmission X-ray microscopy coupled with near-edge X-ray absorption fine structure spectroscop
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Particle Formation from Pulsed Laser Irradiation of SootAggregates studied with scanning mobility particle sizer, transmissionelectron microscope and near-edge x-ray absorption fine structure.
We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes
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Particle Formation from Pulsed Laser Irradiation of Soot Aggregates studied with scanning
We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes
Microscopic Characterization of Carbonaceous Aerosol Particle Aging in the Outflow from Mexico City
This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City Metropolitan Area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (~;;29 km and ~;;65 km, respectively), the fraction of homogenously mixed organic particles increased in both size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment