Accurate measurement of the T-shaped and linear Ar⋯I2(X,ν″=0) binding energies using vibronic-specific I2(B, ν) fragment velocity-map imaging

► Ion-imaging experiments are utilized to investigate the interactions of Ar + I2. ► Slow fragment velocity imaging is used to measure the product kinetic energies. ► The T-shaped and linear Ar⋯I2 complexes are bound by 250.3 and 240.5 cm−1.