Unexpected concentration dependence of the mass accommodation coefficient of water on aqueous triethylene glycol droplets.

The mass accommodation coefficient αM of water on aqueous triethylene glycol droplets was determined for water mole fractions in the range xmol = 0.1-0.93 and temperatures between 21 and 26 °C from modulated Mie scattering measurement on single optically-trapped droplets in combination with a kinetic multilayer model. αM reaches minimum values around 0.005 at a critical water concentration of xmol = 0.38, and increases with decreasing water content to a value of ≈0.1 for almost pure triethylene glycol droplets, essentially independent of the temperature. Above xmol = 0.38, αM first increases with increasing water content and then stabilises at a value of ≈0.1 at the lowest temperatures, while at the highest temperature its value remains around 0.005. We analysed the unexpected concentration and temperature dependence with a previously proposed two-step model for mass accommodation which provides concentration and temperature-dependent activation enthalpies and entropies. We suggest that the unexpected minimum in αM at intermediate water concentrations might arise from a more or less saturated hydrogen-bond network that forms at the droplet surface.

Shining New Light on the Kinetics of Water Uptake by Organic Aerosol Particles.

The uptake of water vapor by various organic aerosols is important in a number of applications ranging from medical delivery of pharmaceutical aerosols to cloud formation in the atmosphere. The coefficient that describes the probability that the impinging gas-phase molecule sticks to the surface of interest is called the mass accommodation coefficient, αM. Despite the importance of this coefficient for the description of water uptake kinetics, accurate values are still lacking for many systems. In this Feature Article, we present various experimental techniques that have been evoked in the literature to study the interfacial transport of water and discuss the corresponding strengths and limitations. This includes our recently developed technique called photothermal single-particle spectroscopy (PSPS). The PSPS technique allows for a retrieval of αM values from three independent, yet simultaneous measurements operating close to equilibrium, providing a robust assessment of interfacial mass transport. We review the currently available data for αM for water on various organics and discuss the few studies that address the temperature and relative humidity dependence of αM for water on organics. The knowledge of the latter, for example, is crucial to assess the water uptake kinetics of organic aerosols in the Earth's atmosphere. Finally, we argue that PSPS might also be a viable method to better restrict the αM value for water on liquid water.

Correction: Assessing relative humidity dependent photoacoustics to retrieve mass accommodation coefficients of single optically trapped aerosol particles.

Correction for 'Assessing relative humidity dependent photoacoustics to retrieve mass accommodation coefficients of single optically trapped aerosol particles' by Matus E. Diveky et al., Phys. Chem. Chem. Phys., 2019, 21, 4721-4731, DOI: .

Fundamental investigation of photoacoustic signal generation from single aerosol particles at varying relative humidity.

Photoacoustic (PA) spectroscopy enjoys widespread applications across atmospheric sciences. However, experimental biases and limitations originating from environmental conditions and particle size distributions are not fully understood. Here, we combine single-particle photoacoustics with modulated Mie scattering to unravel the fundamental physical processes occurring during PA measurements on aerosols. We perform measurements on optically trapped droplets of varying sizes at different relative humidity. Our recently developed technique - photothermal single-particle spectroscopy (PSPS) - enables fundamental investigations of the interplay between the heat flux and mass flux from single aerosol particles. We find that the PA phase is more sensitive to water uptake by aerosol particles than the PA amplitude. We present results from a model of the PA phase, which sheds further light onto the dependence of the PA phase on the mass flux phenomena. The presented work provides fundamental insights into photoacoustic signal generation of aerosol particles.

Assessing relative humidity dependent photoacoustics to retrieve mass accommodation coefficients of single optically trapped aerosol particles.

Photoacoustic spectroscopy is widely used to measure the light absorption of aerosols. However, the impact of key factors such as the effect of relative humidity and mass exchange on photoacoustic measurements are still poorly understood. We assess such measurement biases and their physical origin by analysing the photoacoustic signal of single tetraethylene glycol (TEG) particles at varying relative humidities. Our results show a decrease in the photoacoustic signal at elevated relative humidities for small particles (0.8-1.5 µm), while for larger sizes (2.2-3.2 µm) the trend is reversed. We model the photoacoustic signal to interpret the observed behaviour in terms of mass and heat flux contribution. The single particle photoacoustic signal analysis presented in this paper additionally allows for the retrieval of the mass accommodation coefficient. Fitting our experimental data to the theoretical model reveals values of αM ≈ 0.02-0.005 for water on TEG in the temperature range 295-309 K.

Electronic structure and dynamics of torsion-locked photoactive yellow protein chromophores.

The photocycle of photoactive yellow protein (PYP) begins with small-scale torsional motions of the chromophore leading to large-scale movements of the protein scaffold triggering a biological response. The role of single-bond torsional molecular motions of the chromophore in the initial steps of the PYP photocycle are not fully understood. Here, we employ anion photoelectron spectroscopy measurements and quantum chemistry calculations to investigate the electronic relaxation dynamics following photoexcitation of four model chromophores, para-coumaric acid, its methyl ester, and two analogues with aliphatic bridges hindering torsional motions around the single bonds adjacent to the alkene group. Following direct photoexcitation of S1 at 400 nm, we find that both single bond rotations play a role in steering the PYP chromophore through the S1/S0 conical intersection but that rotation around the single bond between the alkene moiety and the phenoxide group is particularly important. Following photoexcitation of higher lying electronic states in the range 346-310 nm, we find that rotation around the single bond between the alkene and phenoxide groups also plays a key role in the electronic relaxation from higher lying states to the S1 state. These results have potential applications in tuning the photoresponse of photoactive proteins and materials with chromophores based on PYP.