Photodissociation and ab initio studies of Mg+(NH3)n, n=1–4: Electronic structure and photoinduced reaction

Photodissociation spectra of Mg+(NH3)n (n=1–4) cluster ions are examined in the wavelength region of 240–1200 nm. From the comparison with the results of ab initio calculations for the structure and the excitation energies of these clusters, the observed absorption bands are assigned to the transitions derived from the P2–2S transition of Mg+ ion. The extensive redshift of the observed spectra is ascribed to the formation of a one-center ion-pair state. In the photolysis of Mg+NH3, NH3+ and Mg+NH2 ions are produced via photoinduced charge transfer and intracluster reaction processes, respectively, in addition to the Mg+ ion generated by the evaporation of ammonia molecules. For n=2, both the intracluster reaction and evaporation are dominant decay processes, while the evaporation is the sole photodissociation channel for larger clusters. The branching fractions of these processes are found to depend strongly on the solvation number n and also on the photolysis wavelength. The energetics and the dynamics of the dissociation processes are discussed in relation to the redox reaction of metal ions.