Perylene diimide (PDI) derivatives functionalized at the ortho-position (αPPID, αPBDT) were synthesized and used as electron acceptors in non-fullerene organic photovoltaic cells. Because of the good planarity and strong πstacking of ortho-functionalized PDI, the αPPID and αPBDT exhibit a strong tendency to form aggregates, which endow the materials with high electron mobility. The inverted OPVs employing αPDI-based compounds as the acceptors and PBT7-Th as the donor give the highest power conversion efficiency (PCE) values: 4.92% for αPBDT-based devices and 3.61% for αPPID-based devices, which are, respectively, 39% and 4% higher than that of their β-substituted counterparts βPBDT and βPPID. Charge separation studies show more efficient exciton dissociation at interfaces between αPDI-based compounds and PTB7-Th. The results suggest that α-substituted PDI derivatives are more promising electron acceptors for organic photovoltaic (OPV) components than β-isomers.

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.

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.

Molecular beam scattering experiments are used to explore collisions of 60 kJ/mol Ne, CD 4 , ND 3 , and D 2 O with long-chain CH 3 -, NH 2 -, and OH-terminated self-assembled monolayers (SAMs) created via the chemisorption of alkanethiols on gold. Time-of-flight measurements for the scattered gases reveal the extent of energy exchange and the propensity for a gas to thermally accommodate with the surface during a collision. Of the four gases studied, Ne transfers the least amount of translational energy into the monolayers and D 2 O the most. Neon atoms recoil from the OH-SAM with an average of 14.4 kJ/mol of energy, while D 2 O retains only 6.4 kJ/mol of its 60 kJ/mol incident energy when scattering from the same surface. Overall, the trend in final translational energies follows the order Ne > CD 4 > ND 3 > D 2 O for scattering from all three SAMs. The observed trend in the energy exchange is correlated with the gas-surface attractive forces, as determined by ab initio calculations. The thermal accommodation efficiencies of the four gases follow the opposite trend. Thermalization for the Ne atoms is nearly negligible for all three monolayers, whereas D 2 O and ND 3 approach near complete accommodation on all of the monolayers studied. The overall energy exchange and thermal accommodation efficiencies also depend markedly on the terminal group of the SAM. For Ne scattering, the trend for the overall energy transfer follows: CH 3 -> NH 2 -≈ OH-SAMs. In contrast, the overall D 2 O energy transfer is greater when colliding with the OH-SAM than the nonpolar CH 3 -SAM. Together, the results show that the extent of energy transfer depends on a balance between the rigidity of the surface, as affected by intrasurface hydrogen bonding, and the strength of the gas-surface attractive forces, as determined by intermolecular interactions.