The ground and first excited states of the I3 radical are characterized by photoelectron spectroscopy of I3 and Ar⋅I3 at 266 nm. The electron affinity of I3 is 4.226±0.013 eV. Based on the recently determined bond dissociation energy of I3, the I3 ground state is bound by 0.143±0.06 eV. The first excited state of I3 lies 0.27 eV above the ground state. A vibrational progression is seen in the ground state band of the I3 photoelectron spectrum. The addition of an argon atom to I3 reduces the contribution of hot bands to the photoelectron spectrum, facilitating the interpretation of the vibrational structure. Simulations indicate that the I3 ground state is linear with a symmetric stretch frequency of 115±5 cm−1 and is likely to be centrosymmetric.

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