New determination of the adiabatic ionization potential of the BaOH radical from laser photoionization-molecular beam experiments and ab initio calculations

MAXIMILIANO ROSSA; IVÁN CABANILLAS-VIDOSA; GUSTAVO A. PINO; JUAN C. FERRERO

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2012 vol. 136 p. 643031 - 643038

0021-9606

The adiabatic ionization potential of the BaOH radical, as generated in a laser vaporization-supersonic expansion source has been determined by laser photoionization experiments to be (4.55 ¡Ó 0.03) eV. This value supports the three lowest out of seven previous experimental estimates, the former ranging from 4.35 to 4.62 eV. The present result is compared to ab initio calculations, as performed using both quantum chemistry at different levels of theory and density functional theory, and trying several effective core potentials and their accompanying basis sets for Ba. The most satisfactory agreement is obtained for either the adiabatic or vertical ionization potentials that derive from post-Hartree-Fock [MP2 and CCSD(T)] treatments of electron correlation, along with consideration of relativistic effects and extensive basis sets for Ba, in both BaOH and BaOH+. Such conclusions extend to the results of related calculations on the Ba?{OH dissociation energies of BaOH and BaOH+, which were performed to help in calibrating the present computational study. Bonding in BaOH/BaOH+, as well as possible sources of discrepancy with previous experimental determinations of the BaOH adiabatic ionization potential are discussed.