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Mass spectrometry and anion photoelectron spectroscopy has been used to study the gas-phaseSN2 reaction involving Br−and CH3I. The anion photoelectron spectra associated with thereaction intermediates of this SN2 reaction are presented. High-level CCSD(T) calculationshave been utilised to investigate the reaction intermediates that may form as a result of theSN2 reaction along various different reaction pathways, including back-side attack and front-side attack. In addition, simulated vertical detachment energies of each reaction intermediatehave been calculated to rationalise the photoelectron spectra.