High-Resolution Ion-Imaging Studies of the Photodissociation of the BrCl+ Cation

The photofragmentation of state-selected BrCl+ cations has been investigated by velocity-map ion-imaging methods. Detailed analyses of the 79Br+ fragment velocities lead to the most precise values yet reported for (i) the spin−orbit coupling constant for the X2Π state, A = −2070 ± 4 cm-1; (ii) the bond dissociation energies of both states of 79Br35Cl+, 25019 ± 4 cm-1 (X2Π3/2) and 22949 ± 2 cm-1 (X2Π1/2); and (iii) the adiabatic ionization thresholds for forming 79Br35Cl+ parent ions in their X2Π3/2 and X2Π1/2 states, 88292 ± 6 and 90362 ± 4 cm-1, respectively.