How CO2 gas accelerates water nucleation at low temperature.

We conducted homogeneous nucleation experiments for dilute binary H2O-CO2 mixtures in Ar-N2 carrier gas with different CO2/H2O ratios at temperatures of 57 and 75 K and total pressures of ∼40 and 70 Pa, respectively. Direct experimental information on the number and type of molecules in the clusters and on the cluster number concentration is obtained by mass spectrometric detection of nucleating clusters that form in the uniform region of Laval expansions. Only homo-molecular water clusters are observed in the mass spectra.

Direct observation of the complex S(IV) equilibria at the liquid-vapor interface.

The multi-phase oxidation of S(IV) plays a crucial role in the atmosphere, leading to the formation of haze and severe pollution episodes. We here contribute to its understanding on a molecular level by reporting experimentally determined pK values of the various S(IV) tautomers and reaction barriers for SO formation pathways. Complementary state-of-the-art molecular-dynamics simulations reveal a depletion of bisulfite at low pH at the liquid-vapor interface, resulting in a different tautomer ratio at the interface compared to the bulk.

Valence Electronic Structure of Interfacial Phenol in Water Droplets.

Biochemistry and a large part of atmospheric chemistry occur in aqueous environments or at aqueous interfaces, where (photo)chemical reaction rates can be increased by up to several orders of magnitude. The key to understanding the chemistry and photoresponse of molecules in and "on" water lies in their valence electronic structure, with a sensitive probe being photoelectron spectroscopy. This work reports velocity-map photoelectron imaging of submicrometer-sized aqueous phenol droplets in the valence region after nonresonant (288 nm) and resonance-enhanced (274 nm) two-photon ionization with femtosecond ultraviolet light, complementing previous liquid microjet studies.

Valence photoelectron imaging of molecular oxybenzone.

An oxybenzone molecule in the gas phase was characterized by mass spectrometry and angle-resolved photoelectron spectroscopy, using both single and multiphoton ionization schemes. A tabletop high harmonic generation source with a monochromator was used for single-photon ionization of oxybenzone with photon energies of up to 35.7 eV.

Out-of-focus spatial map imaging of magnetically deflected sodium ammonia clusters.

This paper introduces out-of-focus spatial map imaging (SMI) as a detection method for magnetic deflection of molecular/cluster beams, using Na(NH) to illustrate its capabilities. This method enables imaging of the complete spatial distribution, simplifying measurements and allowing for cluster-size-resolved analysis by shifting away from traditional in-focus SMI conditions. Incorporating out-of-focus SMI with TOF-MS and velocity map imaging into a single setup allows for direct assessment of clusters' magnetic moments without needing to pre-select velocities.

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

The mass accommodation coefficient of water on aqueous triethylene glycol droplets was determined for water mole fractions in the range = 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.

Ion imaging of spatially inhomogeneous nanoplasmas in NaCl particles.

Studying photoemission from free, unsupported aerosol particles is a powerful method for gaining insight into light-matter interactions at the nanoscale. We used single-shot velocity map imaging to experimentally measure kinetic energy and angular distributions of ions emitted following interaction of sub-micrometer NaCl particles with femtosecond pulses of near infrared (NIR, 800 nm) and ultraviolet (UV, 266 nm) light. We combined this with time-dependent simulations of light propagation through the particles and a rate equation approach to computationally address the origin of the observed ion emission.

Comparison of Magnetic Deflection among Neutral Sodium-Doped Clusters: Na(HO), Na(NH), Na(MeOH), and Na(DME).

Using a pulsed Stern-Gerlach deflection experiment, we present the results of a comparative study on the magnetic properties of neutral sodium-doped solvent clusters Na(Sol) with = 1-4 (Sol: HO, NH, CHOH, CHOCH). Experimental deflection ratios are compared with values calculated from molecular dynamics simulations. NaNH and NaHO are deflected as a spin 1/2 system, consistent with spin transitions occurring on a time scale significantly longer than 100 μs.

Solvated dielectrons from optical excitation: An effective source of low-energy electrons.

Low-energy electrons dissolved in liquid ammonia or aqueous media are powerful reducing agents that promote challenging reduction reactions but can also cause radiation damage to biological tissue. Knowledge of the underlying mechanistic processes remains incomplete, particularly with respect to the details and energetics of the electron transfer steps. In this work, we show how ultraviolet (UV) photoexcitation of metal-ammonia clusters could be used to generate tunable low-energy electrons in situ.

Hygroscopic growth of single atmospheric sea salt aerosol particles from mass measurement in an optical trap.

Sea salt aerosol is among the most abundant aerosol species in Earth's atmosphere, and its hygroscopicity is an important parameter to quantify its interaction with solar radiation. Conflicting values for the hygroscopic growth have been reported in the literature, which decreases the accuracy with which their impact on Earth's climate can be modelled. Here we report new values of the hygroscopic growth for a selection of salt compositions representative of atmospheric sea salt.

Mutual independence of water and n-nonane nucleation at low temperatures.

The interaction of water with different substances in the earth's atmosphere lies at the heart of many processes that influence our climate. However, it is still unclear how different species interact with water on the molecular level and in which ways this interaction contributes to the water vapor phase transition. Here, we report the first measurements of water-nonane binary nucleation in the 50-110 K temperature range, along with unary nucleation data of both.

Charge Effects on the Photodegradation of Single Optically Trapped Oleic Acid Aerosol Droplets.

It has recently been reported that reactions can occur faster in microdroplets than in extended condensed matter. The electric charge of droplets has also been suggested as a possible cause of this phenomenon. Here, we investigate the influence of electric charges on the photodegradation of single, optically trapped oleic acid aerosol droplets in the absence of other reactive species.

Photoionization of the aqueous phase: clusters, droplets and liquid jets.

This perspective article reviews specific challenges associated with photoemission spectroscopy of bulk liquid water, aqueous solutions, water droplets and water clusters. The main focus lies on retrieving accurate energetics and photoelectron angular information from measured photoemission spectra, and on the question how these quantities differ in different aqueous environments. Measured photoelectron band shapes, vertical binding energies (ionization energies), and photoelectron angular distributions are influenced by various phenomena.

Time-dependent photoemission from droplets: influence of size and charge on the photophysics near the surface.

Photoemission from submicrometer droplets containing a mixture of dioctyl phthalate and dioctyl sebacate was investigated by femtosecond and nanosecond photoionization. Photoelectron spectra recorded after ionization with single 4.7 eV femtosecond or nanosecond laser pulses showed marked differences between the two cases.

Amplification of light within aerosol particles accelerates in-particle photochemistry.

Optical confinement (OC) structures the optical field and amplifies light intensity inside atmospheric aerosol particles, with major consequences for sunlight-driven aerosol chemistry. Although theorized, the OC-induced spatial structuring has so far defied experimental observation. Here, x-ray spectromicroscopic imaging complemented by modeling provides direct evidence for OC-induced patterning inside photoactive particles.

Surface solvation of Martian salt analogues at low relative humidities.

Salt aerosols play important roles in many processes related to atmospheric chemistry and the climate systems on both Earth and Mars. Complicated and still poorly understood processes occur on the salt surfaces when interacting with water vapor. In this study, ambient pressure X-ray photoelectron spectroscopy (APXPS) is used to characterize the surface chemical environment of Martian salt analogues originating from saline lakes and playas, as well as their responses to varying relative humidities.

Shells in CO clusters.

Abundance spectra of (CO) clusters up to ≈ 500 acquired under a wide range of adiabatic expansion conditions are analyzed within the evaporative ensemble framework. The analysis reveals that the cluster stability functions display a strikingly universal pattern for all expansion conditions. These patterns reflect the inherent properties of individual clusters.

Size-Resolved Electron Solvation in Neutral Water Clusters.

Cluster-size-resolved ultrafast dynamics of the solvated electron in neutral water clusters with = 3 to ∼200 molecules are studied with pump-probe time-of-flight mass spectrometry after below band gap excitation. For the smallest clusters, no longer-lived (>100-200 fs) hydrated electrons were detected, indicating a minimum size of ∼ 14 for being able to sustain hydrated electrons. Larger clusters show a systematic increase of the number of hydrated electrons per molecule on the femtosecond to picosecond time scale.

New Particle Formation from the Vapor Phase: From Barrier-Controlled Nucleation to the Collisional Limit.

Studies of vapor phase nucleation have largely been restricted to one of two limiting cases-nucleation controlled by a substantial free energy barrier or the collisional limit where the barrier is negligible. For weakly bound systems, exploring the transition between these regimes has been an experimental challenge, and how nucleation evolves in this transition remains an open question. We overcome these limitations by combining complementary Laval expansion experiments, providing new particle formation data for carbon dioxide over a uniquely broad range of conditions.

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, α. Despite the importance of this coefficient for the description of water uptake kinetics, accurate values are still lacking for many systems.

How volatile components catalyze vapor nucleation.

Gas phase nucleation is a ubiquitous phenomenon in planetary atmospheres and technical processes, yet our understanding of it is far from complete. In particular, the enhancement of nucleation by the addition of a more volatile, weakly interacting gaseous species to a nucleating vapor has escaped molecular-level experimental investigation. Here, we use a specially designed experiment to directly measure the chemical composition and the concentration of nucleating clusters in various binary CO-containing vapors.

Magnetic deflection of neutral sodium-doped ammonia clusters.

We describe the setup and the performance of a new pulsed Stern-Gerlach deflector and present results for small sodium-doped ammonia clusters Na(NH3)n (n = 1-4) in a molecular beam. NaNH3 shows the expected deflection of a spin ½ system, while all lager clusters show much smaller deflections. Experimental deflection ratios are compared with the values calculated from molecular dynamics simulations.

Below Band Gap Formation of Solvated Electrons in Neutral Water Clusters?

Below band gap formation of solvated electrons in neutral water clusters using pump-probe photoelectron imaging is compared with recent data for liquid water and with above band gap excitation studies in liquid and clusters. Similar relaxation times on the order of 200 fs and 1-2 ps are retrieved for below and above band gap excitation, in both clusters and liquid. The independence of the relaxation times from the generation process indicates that these times are dominated by the solvent response, which is significantly slower than the various solvated electron formation processes.

Carbon dioxide and propane nucleation: the emergence of a nucleation barrier.

We investigate homogeneous gas-phase nucleation of CO2 and C3H8 in the uniform postnozzle flow of Laval expansions in the temperature range of 31.2 K to 62.9 K and 32.