Solvated metal cation photochemistry. Electronic state-selective reaction versus evaporation in Sr+(CH3OH)/Sr+(CH3OD)

We present a study of the photodissociation spectrum of Sr+(CH3OH)/Sr+(CH3OD) ions, yielding Sr+ by evaporation and SrOH+/SrOD+ by reaction. The two highest energy bands are 5pπ electronic states and yield 90% SrOH+/SrOD+ products. The three lower energy bands show vibrational structure that can be assigned to SrO stretching and Sr-solvent wagging motions. The reactive fraction of the photodissociation yield shows a strong anticorrelation with sharp resonances in the spectrum, likely arising from competition between rapid reaction and evaporation on the ground state surface and a slower reactive process occurring on an excited surface.