The new peaks, J1/J2 clearly demonstrate the influence of the bromine atom on the 1sC*→σ*(C*-Br) transition in BrBz + and maybe some contribution from 1sC→σ*(C-Br) transition. Thus, the ionization from the π(6b2) orbital, which has bromine character has an impact on the C*-Br bond length and charge distribution near C*-Br bond, leading to a higher transition probability for 1sC*→σ*(C*-Br). Moreover, the experimental and calculated spectra show a strong influence on the core to valence transition energy of the C*-Br bond length that is altered from the relaxed geometry of the BrBz + and from the C*-Br vibrational stretching mode, which is highly active in BrBz + . On the other hand, the influence of the bromine atom on the rest of the benzene ring, and in particular on the transition to the π* orbital, is small.