Vibrational and electronic structure of the 3d(-1)-> 4p(pi,sigma)(-2) normal Auger spectrum of HBr studied by fully relativistic configuration-interaction calculations - art. no. 032712

Fully relativistic, self-consistent field calculations, based on the Dirac- Coulomb-Gaunt Hamiltonian, were performed on the ground state of HBr, the B r 3d-ionized HBr+, and the 4p(pi,sigma)(-2) states of HBr2+. Correlation in the ground and valence-excited states and partially in the Br 3d ionized s tates was described using a configuration-interaction (CI) method. Calculat ed ionization energies and bond lengths were found to be in good agreement with recent experimental results. The distortion in the vibrational bands o f the 3d(-1)-->4p pi(-2) Auger transitions due to lifetime vibrational inte rference was verified through ab initio calculations. Bands due to the tran sitions to bound and continuum vibrational states of the same electronic st ate were reproduced by calculations and compared with experimentally determ ined profiles. The nonadiabatic effects in the spin-orbit-induced avoided l evel crossing were investigated using adiabatic and diabatic electronic bas is sets.