Rotational-resolved pulsed field ionization photoelectron bands for H2+(X2Σg+, v+ = 0, 2, 9, and 11)

We present here the assignment and simulation of rotational transitions for the H-2(+) (X-2 Sigma(g)(+), upsilon(+) = 0,2,9 and 11) vibronic bands using the Buckingham-Orr-Sichel (BOS) model. The simulation shows that perturbation of PFI-PE rotational line intensities due to near-resonance autoionization decreases as upsilon(+) increases. Experimental rotational constants for H-2(+) (X-2 Sigma(g)(+), upsilon(+) = 0,2,9 and 11) are determined with higher accuracy than those obtained in previous HeI and NeI photoelectron studies. In agreement with previous experimental and theoretical investigations, only the Delta N=0 and +/-2 rotational branches are observed in the PFI-PE spectrum for H-2. (C) 1998 Elsevier Science B.V. All rights reserved.