UV photodissociation of H

Aims. Prior investigations into the photodissociation dynamics of the hydrogen molecular ion (H2+) have frequently neglected the impact of shape resonances, which could potentially lead to inaccuracies in astrophysical modeling. This study systematically explores the photodissociation cross sections of H2+ with a rigorous consideration of shape resonances. We aim to elucidate comprehensively the photodissociation mechanisms by accurately accounting for transitions from the electronic ground state 12Σg+ to multiple electronically excited states. Our results provide updated, precise cross-sectional data essential for refining chemical evolution models of interstellar environments and for rectifying previous methodological oversights. Methods. We employed high-level ab initio calculations based on the multireference single- and double-excitation configuration interaction (MRDCI) method to determine the electronic structure of the H2+ ion accurately. The photodissociation cross sections were calculated under the assumption of local thermodynamic equilibrium (LTE) across photon wavelengths ranging from 25 nm to the dissociation threshold, incorporating contributions from the majority of rovibrational states of the ground electronic state. Particular attention was given to analyzing the effects of shape resonances, especially the significant role played by the 12Πu state near the spectral region of the Lyman α line. Results. Our computed cross sections clearly demonstrate that shape resonances substantially influence the photodissociation dynamics of H2+ near the Lyman α line. The contribution from the 12Πu excited state prominently shapes the spectral absorption features around the Lyman α region. These refined theoretical results offer substantial improvements over previous datasets, delivering the precise spectral information necessary for astrophysical simulations, modeling ultraviolet-driven chemical processes in interstellar media, and enhancing our understanding of photochemical dynamics in the early universe.