Impact of Atomic Substitution on Core-Hole Relaxation Dynamics: A Study of Br₂ and IBr

Understanding inner-shell decay processes in heavy-element molecules is essential for unraveling x-ray-induced photodynamics and advancing molecular imaging techniques.  In this study, we investigate the influence of atomic substitution on core-hole relaxation dynamics and molecular fragmentation in Br₂ and IBr, initiated by x-ray absorption at the Br K-edge.  Using a combination of X-ray/ion coincidence measurements and Monte Carlo/molecular dynamics simulations, we track charge distribution and the kinetic energy release (KER) of fragment ions with a total charge from 2+ to 8+. For both molecules, the simulated KER values show good agreement with experiment across different fragmentation channels.  Our comparison reveals that substituting Br with the heavier I atom in IBr has minimal impact on the inner-shell electronic decay process, but significantly influences nuclear motion, leading to slower dissociation, thereby a KER close to the Coulomb limit—an effect attributed to the atomic mass. These findings highlight the interplay between electronic and nuclear effects in molecular fragmentation, particularly in heavy-element species, and provide new insights into medical therapies, structural biology, and astrophysics.