Effect of Hydration on Electron Attachment to Methanesulfonic Acid Clusters

We report an experimental and computational study of the electron-induced chemistry of methanesulfonic acid (MSA, MeSO₃H) in clusters. We combine the mass spectra after the 70 eV electron ionization with the negative ion spectra after electron attachment (EA) at low electron energies of 0-15 eV of the MSA molecule, small MSA clusters, and microhydrated MSA clusters to reveal the solvation effects. The MSA/He coexpansion only generates small MSA clusters with up to four molecules, but adding water substantially hydrates the MSA clusters, resulting in clusters composed of 1-2 MSA molecules accompanied by quite a few water molecules. The clustering strongly suppresses the fragmentation of the MSA molecules upon both the positive ionization and EA. The electron-energy-dependent ion yield for different negative ions is measured. For the MSA molecule and pure MSA clusters, EA leads to an H-abstraction yielding MeSO₃^-. It proceeds efficiently at low electron energies below 2 eV with a shoulder at 3-4 eV and a broad, almost 2 orders of magnitude weaker, peak around 8 eV. The hydrated (H₂O)MeSO₃^- ions with n ≤ 3 exhibit only a broad peak around 7 eV similar to EA of pure water clusters. Thus, for the small clusters, the electron attachment and hydrogen abstraction from water occur. On the other hand, the larger clusters with n > 4 display a peak below 2 eV, which quickly dominates the spectrum with increasing n. This peak is related to the formation of the H₃O⁺·MeSO₃^- ion pair upon hydration and subsequent dipole-supported electron attachment followed by the hydronium neutralization and H₃O^• radical dissociation. The size-resolved experimental data indicate that the ionic dissociation of MSA starts to occur in the neutral MeSO₃H(H₂O) clusters with about four water molecules.