Adiabatic and nonadiabatic effects of nuclear dynamics in spectra of decaying states: Auger spectrum of HF

Abstract

An all ab initio calculation of the Auger spectrum of HF is presented which includes the effects introduced by nuclear dynamics. The involved potential curves of the core-ionized decaying state and the dicationic final states are computed by CASSCF. On these curves, the wave-packet dynamics is performed in an exact manner. Special attention is paid to the transition to the 1Π(2σ−1,1π−1) final state where an avoided crossing between this state and a satellite state is found within the region of decay. By vibronic coupling, the satellite gains intensity which influences the shape of the spectrum. The experimental spectrum is very well reproduced.