De-excitation dynamics of Rydberg states in O-2: II. Vibrational and rotational structure of 2 sigma(-1)(u)(c(4)Sigma(-)(u))(nsd)sigma(g) (3)Sigma(-)(u)(nu=0, 1) states

摘要

The competition between autoionization and neutral dissociation (ND) of the vibronic Rydberg states 2sigma(u)(-1) (c (4)Sigma(u)(-))(nsd)sigma(g) (3)Sigma(u)(-)(upsilon = 0, 1) has been investigated using an experiment of photon-induced fluorescence spectroscopy (PIFS) and the simultaneous measurement of the photo ion yield. The experiments were performed with monochromatized synchrotron radiation from BESSY II with a very narrow bandwidth of DeltaE = 1.5 meV at 23 eV where it was possible to observe single rotational branches. The experiments are compared to ab initio calculations for the partial autoionization and dissociation widths and to the corresponding simulations of the spectroscopic shape of the rovibronic branches. For more precise calculations of the dissociation widths. diabatic potential curves of the 2sigma(u)(-1) (c (4)Sigma(u)(-)) states of the O-2(+) are extracted from the adiabatic ones and improved calculations for molecular orbitals of the Rydberg and Auger electrons are used.