Relaxation dynamics of SF6 studied by energy-resolved electron ion coincidence technique

The mass spectra from the SF6 molecule acquired by energy-resolved electron ion coincidence (EREICO) technique using (1t1g + [5t1u,1t2u]), (3eg + 1t2g), 4t1u, and 5a1g electrons after both valence and S 2p−1 6a1g core excitation reveal a strong selectivity in the dissociation from these states. From the comparison of the obtained spectra, the influence of the core-excited state in the relaxation pathway of the molecule is studied. The S 2p → 6a1g core excitation does not affect the relaxation dynamics after participator Auger decay to the (1t1g + [5t1u,1t2u])−1 and (4t1u)−1 states, but it alters the relaxation dynamics after participator Auger decay to the (3eg + 1t2g)−1 and (5a1g)−1 states with respect to the decay processes after direct excitation of the same orbitals. These observations point to core excitation induced dissociation in the SF6 molecule.