A velocity-map imaging study of methyl non-resonant multiphoton ionization from the photodissociation of CH3I in the A-band

Chemical reaction dynamics and, particularly, photodissociation in the gas phase are generally studied using pump-probe schemes where a first laser pulse induces the process under study and a second one detects the produced fragments. Providing an efficient detection of ro-vibrationally state-selected photofragments, the resonance enhanced multiphoton ionization (REMPI) technique is, without question, the most popular approach used for the probe step, while non-resonant multiphoton ionization (NRMPI) detection of the products is scarce. The main goal of this work is to test the sensitivity of the NRMPI technique to fragment vibrational distributions arising from molecular photodissociation processes. We revisit the well-known process of methyl iodide photodissociation in the A-band at around 280 nm, using the velocity-map imaging technique in conjunction with NRMPI of the methyl fragment. The detection wavelength, carefully selected to avoid any REMPI transition, was scanned between 325 and 335nm seeking correlations between the different observables-the product vibrational, translational and angular distributions-and the excitation wavelength of the probe laser pulse. The experimental results have been discussed on the base of quantum dynamics calculations of photofragment vibrational populations carried out on available ab initio potential-energy surfaces using a four-dimensional model.Peer Reviewe

A velocity-map imaging study of the non-resonant multiphoton ionization detection of methyl photofragments from the photodissociation of CH3I in the A-band

MOLEC 2016, Toledo (Spain), 11 - 16 September 2016N