[3+2] resonance enhanced multiphoton ionization of I and Br formed from the infrared multiphoton decomposition of CF3I and CF3Br

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Abstract
Resonance enhanced multiphoton ionization (REMPI) has been used to study the products of the infrared multiphoton decomposition (IRMPD) of CF3I in a very low‐pressure photolysis (VLPΦ) cell. The strongest REMPI signals are due to the ground state I(2P3/2) and the spin–orbit excited state I*(2P1/2). The origins of I and I* were determined from the time and IR laser fluence dependences of the REMPI signal. I* is formed by visible single photon dissociation of vibrationally excited CF3I and by visible multiphoton dissociation of I2 and thermal CF3I. The ionization efficiency of I has been determined relative to NH3 for our probe laser conditions, and the sticking coefficient of I with gold surfaces has been determined. The REMPI spectra of the products of the IRMPD of CF3Br is also presented.