Photodissociation spectra of Mg+(H2O)n (n = 1-5) cluster ions were examined in the wavelength region from 720 to 250 mn by monitoring the total yield of the fragment ions. The absorption bands exhibit redshifts as large as 17 000 cm-1 with respect to the 2P-2S resonance line of the free Mg+ ion and were explained by the shift of this transition as a result of hydration. The spectra also exhibit clear evolution of solvation shell with the first shell closing at n = 3, being consistent with the theoretical prediction. The mass spectra of the fragment ions show the existence of two dissociation processes: the evaporation of water molecules and the photoinduced intracluster reaction to produce the hydrated MgOH+ ion, MgOH+(H2O)m. The branching fraction between the two processes depends strongly on the solvent number n and also on the photolysis wavelength. The energetics and the dynamics of the dissociation processes were discussed in conjunction with the results of ab initio calculations.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry