Photoionization and Photofragmentation Dynamics of I(2) in Intense Laser Fields: A Velocity-Map Imaging Study

[Image: see text] The photoionization and photofragmentation dynamics of I(2) in intense femtosecond near-infrared laser fields were studied using velocity-map imaging of cations, electrons, and anions. A series of photofragmentation pathways originating from different cationic electronic states were observed following single ionization, leading to I(+) fragments with distinct kinetic energies, which could not be resolved in previous studies. Photoelectron spectra indicate that these high-lying dissociative states are primarily produced through nonresonant ionization from several molecular orbitals (MO) of the neutral. The photoelectron spectra also show clear signatures of resonant ionization pathways (Freeman resonances) to low-lying bound ionic states via Rydberg states of the neutral moiety. To investigate the role of these Rydberg states further, we imaged anionic products (I(–)) formed through ion-pair dissociations of neutral molecules excited to these Rydberg states by the intense femtosecond laser pulse. Collectively, these results shed significant new light on the complex dynamics of I(2) molecules in intense laser fields and on the important role of neutral Rydberg states in a full description of strong-field phenomena in molecules.