Resolving electronic evolution during bond dissociation

Abstract

Coupled electronic and nuclear motions govern chemical reactions, yet resolving how electronic structure evolves during bond dissociation remains a central challenge. Here we investigate the photodissociation of Br2 using correlated photoelectron photoion coincidence measurements. A 400 nm pulse initiates dissociation, while strong field ionization probes the evolving molecular system. Coincident measurement of three dimensional photoion and photoelectron momenta provides simultaneous access to the internuclear separation and the accompanying electronic evolution. We identify multiple distinct stages of electronic evolution during bond dissociation. The reshaping of the ionizing molecular orbital occurs first, followed by redistribution and localization of the electronic charge density, and finally by the gradual decay of residual electronic coherence between the separating atomic centers. Between the molecular and atomic limits, we observe an intermediate bond-breaking state in which localized atomic character coexists with a partially delocalized electronic response. By combining correlated observables with semiclassical modelling, we resolve the temporal ordering of these coupled electronic and nuclear processes and determine their associated dynamical timescales. These results demonstrate how correlated momentum observables can disentangle different aspects of the molecular-to-atomic transition.

21 pages, 4 figures