Eur. Phys. J. D 11, 207-212 (2000)
https://doi.org/10.1007/s100530070085

Predissociation resonances in CO and IBr. Smooth exterior scaling combined with the discrete variable representation

Department of Quantum Chemistry, Uppsala University, Box 518, 751 20 Uppsala, Sweden

Received: 12 July 1999
Revised: 6 December 1999
Published online: 15 August 2000

Abstract

Smooth exterior scaling (SES) and the discrete variable representation (DVR) are combined to accurately compute predissociation resonances of a bound state non-adiabatically coupled to a dissociative state. For the CO( predissociation interaction good agreement is found with approaches based on optical potentials and complex scaling. The comparison is done both in the diabatic and the adiabatic representation. The effect of the coupling strength in the IBr predissociation interaction and the transition from the diabatic to the adiabatic picture was studied by computing resonances for coupling strengths from up to . The transition from weak (diabatic) to strong (adiabatic) coupling was clearly seen. The intermediate case leads to a complicated resonance distribution. Comparison was made with recent studies using pump-probe spectroscopy [M. Shapiro, M.J.J. Vrakking, A. Stolow, J. Chem. Phys. 110, 2465 (1999)]. It was found that the overall features of the experiment could be explained from the resonance distribution, but for a detailed comparison more accurate potential energy surfaces and couplings are needed.