Water molecule elimination from the protonated methanol dimer ion-An example of a size-selective intracluster reaction.

The abundance of extraterrestrial methanol makes the reaction between methanol molecules in a molecular cluster a possible key step in the search for mechanisms for the formation of more complex molecules under the conditions of the interstellar medium as well as circumstellar and planetary atmospheres. The reaction leading to the formation of the dimethyl ether ion from a methanol molecule interacting with a protonated methanol ion via the elimination of a water molecule is a basic mechanism for the formation of complex organic molecules. Here, we experimentally examine such reactions in the gas phase, analyzing the production and reactivity of protonated cluster ions formed by the ionization of a supersonic jet of methanol. Focusing especially on the post-collisional relaxation of the protonated methanol dimer and trimer ions after high-energy single collisions, the results indicate a strong size selectivity favoring the occurrence of this reaction only in the dimer ion. To elucidate this behavior, the velocity distribution of the eliminated water molecule was measured using an event-by-event coincidence analysis. These results are interpreted using quantum chemical calculations of the dissociation pathways. It turns out that in the dimer case, two transition states are able to contribute to this intracluster reaction. In the trimer case, methanol evaporation appears as the most energetically favorable relaxation pathway.

Glycine Peptide Chain Formation in the Gas Phase via Unimolecular Reactions.

Peptide chain formation from amino acids such as glycine is a key step in the emergence of life. Unlike their synthesis by living systems, how peptide chains grow under abiotic conditions is an open question given the variety of organic compounds discovered in various astrophysical environments, comets and meteorites. We propose a new abiotic route in the presence of protonated molecular dimers of glycine in a cold gaseous atmosphere without further need for a solid catalytic substrate. The results provide evidence for the preferential formation of mixed protonated dimers of glycine consisting of a dipeptide and a glycine molecule instead of pure protonated glycine dimers. Additional measurements mimicking a cosmic-ray impact in terms of internal excitation show that a single gas-phase collision induces polymerization via dehydration in both the mixed and pure dimer ions. Peptide chain growth is thus demonstrated to occur via a unimolecular gas-phase reaction in an excited cluster ion.

Energy Dispersion in Pyridinium-Water Nanodroplets upon Irradiation.

Postirradiation dissociation of molecular clusters has been mainly studied assuming energy redistribution in the entire cluster prior to the dissociation. Here, the evaporation of water molecules from out-of-equilibrium pyridinium-water cluster ions was investigated using the recently developed correlated ion and neutral time-of-flight (COINTOF) mass spectrometry technique in combination with a velocity-map imaging (VMI) device. This special setup enables the measurement of velocity distributions of the evaporated molecules upon high-velocity collisions with an argon atom. The distributions measured for pyridinium-water cluster ions are found to have two distinct components. Besides a low-velocity contribution, which corresponds to the statistical evaporation of water molecules after nearly complete redistribution of the excitation energy within the clusters, a high-velocity contribution is also found in which the molecules are evaporated before the energy redistribution is complete. These two different evaporation modes were previously observed and described for protonated water cluster ions. However, unlike in the case of pure water clusters, the low-velocity part of the distributions for pyridinium-doped water clusters is itself composed of two distinct Maxwell-Boltzmann distributions, indicating that evaporated molecules originate in this case from out-of-equilibrium processes. Statistical molecular dynamics simulations were performed to (i) understand the effects caused in the ensuing evaporation process by the various excitation modes at different initial cluster constituents and to (ii) simulate the distributions resulting from sequential evaporations. The presence of a hydrophobic impurity in water clusters is shown to impact water molecule evaporation due to the energy storage in the internal degrees of freedom of the impurity.

A stand-alone magnetic guide for producing tuneable radical beams.

Radicals are prevalent in gas-phase environments such as the atmosphere, combustion systems, and the interstellar medium. To understand the properties of the processes occurring in these environments, it is helpful to study radical reaction systems in isolation-thereby avoiding competing reactions from impurities. There are very few methods for generating a pure beam of gas-phase radicals, and those that do exist involve complex setups. Here, we provide a straightforward and versatile solution. A magnetic radical filter (MRF), composed of four Halbach arrays and two skimming blades, can generate a beam of velocity-selected low-field-seeking hydrogen atoms. As there is no line-of-sight through the device, all species that are unaffected by the magnetic fields are physically blocked; only the target radicals are successfully guided around the skimming blades. The positions of the arrays and blades can be adjusted, enabling the velocity distribution of the beam (and even the target radical species) to be modified. The MRF is employed as a stand-alone device-filtering radicals directly from the source. Our findings open up the prospect of studying a range of radical reaction systems with a high degree of control over the properties of the radical reactants.

Impact of a hydrophobic ion on the early stage of atmospheric aerosol formation.

Atmospheric aerosols are one of the major factors affecting planetary climate, and the addition of anthropogenic molecules into the atmosphere is known to strongly affect cloud formation. The broad variety of compounds present in such dilute media and their specific underlying thermalization processes at the nanoscale make a complete quantitative description of atmospheric aerosol formation certainly challenging. In particular, it requires fundamental knowledge about the role of impurities in water cluster growth, a crucial step in the early stage of aerosol and cloud formation. Here, we show how a hydrophobic pyridinium ion within a water cluster drastically changes the thermalization properties, which will in turn change the corresponding propensity for water cluster growth. The combination of velocity map imaging with a recently developed mass spectrometry technique allows the direct measurement of the velocity distribution of the water molecules evaporated from excited clusters. In contrast to previous results on pure water clusters, the low-velocity part of the distributions for pyridinium-doped water clusters is composed of 2 distinct Maxwell-Boltzmann distributions, indicating out-of-equilibrium evaporation. More generally, the evaporation of water molecules from excited clusters is found to be much slower when the cluster is doped with a pyridinium ion. Therefore, the presence of a contaminant molecule in the nascent cluster changes the energy storage and disposal in the early stages of gas-to-particle conversion, thereby leading to an increased rate of formation of water clusters and consequently facilitating homogeneous nucleation at the early stages of atmospheric aerosol formation.