Vibrationally resolved photoelectron spectroscopy of BO- and BO2-: a joint experimental and theoretical study.

We report a photoelectron spectroscopy and computational study of two simple boron oxide species: BO- and BO2-. Vibrationally resolved photoelectron spectra are obtained at several photon energies (355, 266, 193, and 157 nm) for the 10B isotopomers, 10BO- and 10BO2-. In the spectra of 10BO-, we observe transitions to the 2Sigma+ ground state and the 2Pi excited state of 10BO at an excitation energy of 2.96 eV. The electron affinity of 10BO is measured to be 2.510+/-0.015 eV. The vibrational frequencies of the ground states of 10BO- and 10BO and the 2Pi excited state are measured to be 1725+/-40, 1935+/-30, and 1320+/-40 cm-1, respectively. For 10BO2-, we observe transitions to the 2Pig ground state and two excited states of 10BO2, 2Piu, and 2Sigmau+, at excitation energies of 2.26 and 3.04 eV, respectively. The electron affinity of 10BO2 is measured to be 4.46+/-0.03 eV and the symmetrical stretching vibrational frequency of the 2Piu excited state of 10BO2 is measured to be 980+/-30 cm-1. Both density functional and ab initio calculations are performed to elucidate the electronic structure and chemical bonding of the two boron oxide molecules. Comparisons with the isoelectronic AlO- and AlO2- species and the closely related molecules CO, N2, CN-, and CO2 are also discussed.