Resonant two-photon ionization spectroscopy of jet-cooled PdC

The first optical investigation of the spectra of diatomic PdC has revealed that the ground state has ?=0+, with a bond length of r0=1.712?. The Hund?s case (a) nature of this state could not be unambiguously determined from the experimental data, but dispersed fluorescence studies to be reported in a separate publication, in combination with a comparison to theoretical calculations, demonstrate that it is the 2?4 12?2, 1?+0+ state, which undergoes spin?orbit mixing with a low-lying 2?4 12?1 6rr1, 3II0+ state. An excited 3?+ state with re=1.754?0.003? (r051.758?0.002?) and ?G1/25794 cm-1 is found at T0=17 867 cm21. Although only the ?=1 component of this state is directly observed, the large hyperfine splitting of this state for the 105Pd 12C isotopomer implies that an unpaired electron occupies an orbital that is primarily of 5s character on Pd. Comparison to ab initio calculations identifies this state as 2?4 12?113?1, 3?+1. To higher wavenumbers a number of transitions to states with ?=1+ have been observed and rotationally analyzed. Two groups of these have been organized into band systems, despite the clear presence of homogeneous perturbations between states with ?=0+ in the region between 22 000 and 26 000 cm-1.