Probing the electronic and vibrational structure of Au2Al2(-) and Au2Al2 using photoelectron spectroscopy and high resolution photoelectron imaging.

Abstract

The electronic and vibrational structures of Au2Al2(-) and Au2Al2 have been investigated using photoelectron spectroscopy (PES), high-resolution photoelectron imaging, and theoretical calculations. Photoelectron spectra taken at high photon energies with a magnetic-bottle apparatus reveal numerous detachment transitions and a large energy gap for the neutral Au2Al2. Vibrationally resolved PE spectra are obtained using high-resolution photoelectron imaging for the ground state detachment transition of Au2Al2(-) at various photon energies (670.55-843.03 nm). An accurate electron affinity of 1.4438(8) eV is obtained for the Au2Al2 neutral cluster, as well as two vibrational frequencies at 57 ± 8 and 305 ± 13 cm(-1). Hot bands transitions yield two vibrational frequencies for Au2Al2(-) at 57 ± 10 and 144 ± 12 cm(-1). The obtained vibrational and electronic structure information is compared with density functional calculations, unequivocally confirming that both Au2Al2(-) and Au2Al2 possess C2v tetrahedral structures.