Electronic spectroscopy and excited state mixing of OThF.

Electronic spectra for OThF have been recorded using fluorescence excitation and two-photon resonantly enhanced ionization techniques. Multiple vibronic bands were observed in the 340-460 nm range. Dispersed fluorescence spectra provided ground state vibrational constants and evidence of extensive vibronic state mixing at higher excitation energies. Two-photon ionization measurements established the ionization energy for OThF of 6.283(5) eV. To guide the assignment of the OThF spectra, electronic structure calculations were carried out using relativistic equation-of-motion coupled-cluster singles and doubles methods. These calculations indicated that spin-orbit induced mixing of the 32A″ and 42A' states was mediated by a seam of potential energy surface intersections.