The influence of nuclear volume and electronic structure on the rotational energy of platinum monoxide, PtO

The pure rotational spectra of seven isotopic species of platinum monoxide have been measured with a cavity pulsed jet Fourier-transform microwave spectrometer. The molecules were prepared by laser ablation of Pt foil in the presence of O2 and stabilized in a supersonic jet of argon. A multi-isotopomer Dunham-type analysis of the spectra produced values for Y01 and Y11, along with unusually large values for Born-Oppenheimer breakdown (BOB) parameters for both Pt and O atoms. The values of the BOB parameters have been rationalized in terms of the molecular electronic structure and finite nuclear size (field shift) effects. A large negative 195Pt effective nuclear spin-rotation constant has been rationalized in terms of the electron-nucleus dipole-dipole hyperfine constant. Precise internuclear separations have been evaluated.