Journal of Physical Chemistry A, Vol.114, No.37, 9999-10004, 2010
Ion-Pair Dissociation Dynamics of SO2 in the Photon Energy Range 14.87-15.15 eV
The ion-pair dissociation dynamics of SO2 -> SO+ (X-2 Pi,nu) + O-(2P(J)) in the excitation energy range 14.87-15.15 eV has been studied using the tunable XUV laser and velocity map imaging method. The O-yield spectrum, the translational energy distributions, and the angular distributions of the photofragments have been measured. The electronic structures and selected cuts of potential energy surfaces for the ion-pair states have been calculated by employing the quantum chemistry calculation method at the CASSCF/6-311++g** level. The equilibrium structures of the six ion-pair states all have linear geometries. An orbital correlation diagram was drawn to illustrate the ion-pair dissociation mechanism. Combining the experimental and theoretical results, it is concluded that the ion-pair dissociation takes place mainly via the predissociation of Rydberg states (1)A(1) [((CB1)-B-2)4db(1)] and (1)A(1) [(D(2)A(1))4sa(1)]. The experimental results confirm the previous theoretical calculation results about the symmetry assignments for the energy sequence of SO2+ as C(B-2(1)) < D((2)A(1)),