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Jan Poštulka1, Petr Slavíček2, Alicja Domaracka3

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Researchers studied pinene-water clusters using electron impact and photoionization. They found different cluster formations, revealing insights into proton transfer and atmospheric water cluster stabilization.

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Area of Science:

  • Atmospheric Chemistry
  • Physical Chemistry
  • Cluster Science

Background:

  • Understanding the formation and stabilization of atmospheric water clusters is crucial for cloud physics.
  • Pinene-water interactions play a role in atmospheric aerosol formation, potentially influencing cloud condensation nuclei (CCN) production.

Purpose of the Study:

  • To investigate the ionization mechanisms of small mixed pinene-water clusters.
  • To elucidate the pathways leading to protonated water cluster formation.
  • To determine the role of pinene in water cluster stabilization and its implications for atmospheric processes.

Main Methods:

  • Ionization of mixed pinene-water clusters using electron impact and "fragmentation-free" photoionization after sodium doping.
  • Analysis of cluster cations using mass spectrometry.
  • Theoretical investigation using ab initio calculations to model proton transfer pathways.

Main Results:

  • Electron ionization produced pure pinene, mixed pinene-water, and protonated water cluster cations.
  • Photoionization yielded only water-Na+ clusters, with a smaller mean cluster size compared to electron ionization.
  • Protonated water clusters form both directly and indirectly via pinene ionization, with proton transfer feasibility confirmed by calculations.

Conclusions:

  • Proton transfer from pinene to water clusters is a significant pathway, especially for larger clusters.
  • Proton solvation energy in finite-size clusters controls the proton transfer reaction.
  • The observed stabilization mechanism of water clusters by pinene may contribute to atmospheric cloud condensation nuclei formation.