Low-temperature Bessel beam trap for single submicrometer aerosol particle studies.

We report on a new instrument for single aerosol particle studies at low temperatures that combines an optical trap consisting of two counter-propagating Bessel beams (CPBBs) and temperature control down to 223 K (-50 °C). The apparatus is capable of capturing and stably trapping individual submicrometer- to micrometer-sized aerosol particles for up to several hours. First results from studies of hexadecane, dodecane, and water aerosols reveal that we can trap and freeze supercooled droplets ranging in size from ~450 nm to 5500 nm (radius). We have conducted homogeneous and heterogeneous freezing experiments, freezing-melting cycles, and evaporation studies. To our knowledge, this is the first reported observation of the freezing process for levitated single submicrometer-sized droplets in air using optical trapping techniques. These results show that a temperature-controlled CPBB trap is an attractive new method for studying phase transitions of individual submicrometer aerosol particles.

Gas-surface reactions of nitrate radicals with vinyl-terminated self-assembled monolayers.

Interfacial reactions between gas-phase nitrate radicals, a key nighttime atmospheric oxidant, and a model unsaturated organic surface have been investigated to determine the reaction kinetics and probable reaction mechanism. The experimental approach employs in situ reflection-absorption infrared spectroscopy (RAIRS) to monitor bond rupture and formation while a well-characterized effusive flux of NO3 impinges on the organic surface. Model surfaces are created by the spontaneous adsorption of vinyl-terminated alkanethiols (HS(CH2)16CHCH2) onto a polycrystalline gold substrate. The H2C=CH-terminated self-assembled monolayers provide a well-defined surface with the double bond positioned precisely at the gas-surface interface. The surface reaction kinetics obtained from RAIRS revealed that the consumption rate of the terminal vinyl groups is nearly identical to the formation rate of a surface-bound nitrate species and implies that the mechanism is one of direct addition to the vinyl group rather than hydrogen abstraction. Upon nitrate radical collisions with the surface, the initial reaction probability for consumption of carbon-carbon double bonds was determined to be (2.3 ± 0.5) × 10(-3). This reaction probability is approximately two orders of magnitude greater than the probability of ozone reactions on the same surface, which suggests that oxidation of surface-bound vinyl groups by nighttime nitrate radicals may play an important role in atmospheric chemistry despite their relatively low concentration.

Timescales of water transport in viscous aerosol: measurements on sub-micron particles and dependence on conditioning history.

Evaporation studies of single aqueous sucrose aerosol particles as a function of relative humidity (RH) are presented for coarse and fine mode particles down into the submicron size range (600 nm < r < 3.0 µm). These sucrose particles serve as a proxy for biogenic secondary organic aerosols that have been shown to exist, under ambient conditions, in an ultraviscous glassy state, which can affect the kinetics of water mass transport within the bulk phase and hinder particle response to changes in the gas phase water content. A counter-propagating Bessel beams (CPBBs) optical trapping setup is employed to monitor the real-time change in the particle radius with RH decreasing from 75% to 5%. The slow-down of the size change upon each RH step and the deviation from the theoretical equilibrium hygroscopic growth curve indicate the onset of glassy behavior in the RH range of 10-40%. Size-dependent effects were not observed within the uncertainty of the measurements. The influence of the drying time below the glass transition RH on the timescale of subsequent water condensation and re-equilibration for sucrose particles is explored by optical tweezers measurements of micron-sized particles (3 µm < r < 6 µm). The timescale for water condensation and re-equilibration is shown to increase with increasing drying time, i.e. the time over which a viscous particle is dried below 5% RH. These studies demonstrate the importance of the history of the particle conditioning on subsequent water condensation and re-equilibration dynamics of ultraviscous and glassy aerosol particles.

Gas-surface scattering dynamics of CO2, NO2, and O3 in collisions with model organic surfaces.

High-energy (70 kJ/mol) molecular beams of CO(2), NO(2), and O(3) were scattered from long-chain methyl (CH(3)-), hydroxyl (OH-), and perfluoro (CF(3)(CF(2))(8)-, or F-) ω-functionalized alkanethiol self-assembled monolayers (SAMs) on gold to study the dynamics of energy exchange and thermal accommodation of atmospherically important triatomic molecules on model organic surfaces. Overall, the extent of energy transfer in gas collisions with all of the surfaces studied was substantial. Specifically, the triatomics scatter from each surface only after dissipating greater than 80% of their incident energy. Furthermore, although the OH-SAM is a more rigid surface, the extent of energy transfer and accommodation of these molecules to the CH(3)- and OH-SAMs were approximately the same. The similar scattering dynamics are likely due to significant gas-surface attractive forces between the triatomics and the OH terminal groups, which compensate for the rigidity of this monolayer. In contrast to the OH- and CH(3)-SAMs, the dominant pathway in collisions of the gases with the F-SAM was impulsive scattering. The portion of molecules that accommodated (<40%) to the F-SAM was about half of the amount that accommodated (∼70%) to the CH(3)- and OH-SAMs. Although differences in the surface properties had a significant effect on the dynamics, variances in the chemical and physical properties of the three gases, CO(2), NO(2), and O(3), were found to have little effect on the extent of energy transfer and accommodation for collisions with any one surface.

Changes in the optical properties of benzo[a]pyrene-coated aerosols upon heterogeneous reactions with NO2 and NO3.

Chemical reactions can alter the chemical, physical, and optical properties of aerosols. It has been postulated that nitration of aerosols can account for atmospheric absorbance over urban areas. To study this potentially important process, the change in optical properties of laboratory-generated benzo[a]pyrene (BaP)-coated aerosols following exposure to NO(2) and NO(3) was investigated at 355 nm and 532 nm by three aerosol analysis techniques. The extinction coefficient was determined at 355 nm and 532 nm from cavity ring-down aerosol spectroscopy (CRD-AS); the absorption coefficient was measured by photoacoustic spectroscopy (PAS) at 532 nm, while an on-line aerosol mass spectrometer (AMS) supplied real-time quantitative information about the chemical composition of aerosols. In this study, 240 nm polystyrene latex (PSL) spheres were thinly coated with BaP to form 300 or 310 nm aerosols that were exposed to high concentrations of NO(2) and NO(3) and measured with CRD-AS, PAS, and the AMS. The extinction efficiencies (Q(ext)) changed after exposure to NO(2) and NO(3) at both wavelengths. Prior to reaction, Q(ext) for the 355 nm and 532 nm wavelengths were 4.36 ± 0.04 and 2.39 ± 0.05, respectively, and Q(ext) increased to 5.26 ± 0.04 and 2.79 ± 0.05 after exposure. The absorption cross-section at 532 nm, determined with PAS, reached σ(abs) = (0.039 ± 0.001) × 10(-8) cm(2), indicating that absorption increased with formation of nitro-BaP, the main reaction product detected by the AMS. The single-scattering albedo (SSA), a measure of particle scattering efficiency, decreased from 1 to 0.85 ± 0.03, showing that changes in the optical properties of BaP-covered aerosols due to nitration may have implications for regional radiation budget and, hence, climate.

Gas-surface energy exchange and thermal accommodation of CO2 and Ar in collisions with methyl, hydroxyl, and perfluorinated self-assembled monolayers.

Molecular beams of CO(2) and Ar were scattered from long-chain methyl (CH(3)-), hydroxyl (OH-), and perfluoro ((CF(2))(7)CF(3)-) functionalized alkanethiol self-assembled monolayers (SAMs) on gold to study the dynamics of energy exchange and thermal accommodation on model organic surfaces. Ar collisions, for incident energies ranging from 25 to 150 kJ mol(-1), exhibit final energy distributions that depend significantly on the terminal functional group of the SAM. The long-chain CH(3)-terminated monolayers serve as an excellent energy sink for dissipating the incident translational energy. For example, at 150 kJ mol(-1), greater than 90% of the collision energy is transferred to the CH(3)-SAM surface for specularly-scattered atoms (θ(i) = θ(f) = 30° from normal). However, the OH-SAM is a more rigid collision partner due to the formation of an intra-monolayer hydrogen bonding network and the (CF(2))(7)CF(3)-SAM (F-SAM) provides a high degree of rigidity due to the massive CF(3) groups. The final energies for the triatomic, CO(2), scattering from the three surfaces are remarkably similar to the results for Ar scattering. The only significant difference in the translational energy transfer dynamics for these two gases appears in collisions with the OH-SAM. Strong gas-surface attractive forces between CO(2) and the OH-SAM surface appear to counter the rigidity of the hydrogen-bonding network to help bring the majority of the molecules to thermal equilibrium at all incident energies up to 150 kJ mol(-1), resulting in increased energy transfer in comparison to Ar. The similarities in energy transfer for Ar and CO(2) final energy distributions in scattering from the CH(3)- and F-SAMs suggest that the internal degrees of freedom in the triatomic play only a small role in determining the outcome of the gas-surface collision under the scattering conditions employed in this work.

Surface plasmon resonance studies of pullulan and pullulan cinnamate adsorption onto cellulose.

Surface plasmon resonance studies showed pullulan cinnamates (PCs) with varying degrees of substitution (DS) adsorbed onto regenerated cellulose surfaces from aqueous solutions below their critical aggregation concentrations. Results on cellulose were compared to PC adsorption onto hydrophilic and hydrophobic self-assembled thiol monolayers (SAMs) on gold to probe how different interactions affected PC adsorption. PC adsorbed onto methyl-terminated SAMs (SAM-CH(3)) > cellulose > hydroxyl-terminated SAMs (SAM-OH) for high DS and increased with DS for each surface. Data for PC adsorption onto cellulose and SAM-OH surfaces were effectively fit by Langmuir isotherms; however, Freundlich isotherms were required to fit PC adsorption isotherms for SAM-CH(3) surfaces. Atomic force microscopy images from the solid/liquid interfaces revealed PC coatings were uniform with surface roughnesses <2 nm for all surfaces. This study revealed hydrogen bonding alone could not explain PC adsorption onto cellulose and hydrophobic modification of water-soluble polysaccharides was a facile strategy for their conversion into surface modifying agents.