Mass-analyzed threshold ionization and structural isomers of M3O4 (M = Sc, Y, and La)

M3O4 (M = Sc, Y, and La) were produced in a pulsed laser-vaporization molecular beam source and studied by mass-analyzed threshold ionization (MATI) spectroscopy and electronic structure calculations. Adiabatic ionization energies (AIEs) of the neutral clusters and vibrational frequencies of the cations were measured accurately for the first time from the MATI spectra. Five possible structural isomers of M3O4 were considered in the calculations and spectral analysis. A cage-like structure in C-3v point group was identified as the most stable one. The structure is formed by fusing three M2O2 fragments together, each sharing two O-M bonds with others. The ground electronic state of the neutral clusters is (2)A(1) with the unpaired electron being largely a metal-based s character. Ionization of the (2)A(1) state yields a (1)A(1) ion state in a similar geometry to the neutral cluster. The AIEs of the clusters are 4.4556 (6), 4.0586(6), and 3.4750(6) eV for M = Sc, Y, and La, respectively. The observed vibrational modes of the cations include metal-oxygen stretching, metal triangle breathing, and oxygen-metal-oxygen rocking in the frequency range of 200-800 cm(-1). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4747530]