Abstract

Interatomic Coulombic decay (ICD) in Ar 2, ArKr and Kr 2 following Ar 2p or Kr 3d Auger decay has been investigated by means of momentum-resolved electron–ion–ion coincidence spectroscopy. This sequential decay leads to Coulombic dissociation into dication and monocation. Simultaneously determining the kinetic energy of the ICD electron and the kinetic energy release between the two atomic ions, we have been able to unambiguously identify the ICD channels. We find that, in general, spin-conserved ICD, in which the singlet (triplet) dicationic state produced via the atomic Auger decay preferentially decays to the singlet (triplet) state, transferring the energy to the other atom, is faster than spin-flip ICD, in which the Auger final singlet (triplet) dicationic state decays to the triplet (singlet) state. However, spin-flip ICD may take place when spin-conserved ICD becomes energetically forbidden. Dipole-forbidden ICDs from K r 2 + ( 4 s − 2 S 1 ) – B (B = Ar or Kr) to K r 2 + ( 4 p − 2 D 1 , P 3 ) – B + are also observed.

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