Two-dimensional REMPI of CF3Br: Rydberg states and photofragmentation channels

► (2 + n) REMPI of CF3Br are studied for the 71 320-84 600 cm−1 excitation region. ► REMPI of CF3Br reveal CF3+, iBr+ and C+ ion signals. ► Resonance excitations to characterised Rydberg states are observed. ► Excitations to Rydberg states are followed by ion-pair formations. ► Predissociation of Rydberg states is observed.