The high repulsive states of HgAr and HgNe van der Waals complexes, correlating with Hg 6s6d atomic states have been investigated by double resonance spectroscopy, through the first excited state A 30 + and B 31 of the complexes. The repulsive potentials have been fitted through numerical Franck-Condon simulations. They have been characterized by perturbative calculation as quasi-pure 6dΣ potentials in Hund's case a. The strong Hg-rare gas electrostatic interaction potential overruns the spin-orbit interaction at distances shorter than 7 Å. These observed repulsive states are mostly of Ω=1 character correlating with 3D3 at infinite distances. The contribution from the potential of Ω=0- symmetry correlating with 1D 2 is of minor importance. Therefore, the absorption in the repulsive states of the complex arises mostly from proximity induced absorption in an optically forbidden transition 3P1→3D 3. A perturbative model accounts well for the bound free absorption intensities experimentally observed.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry