- Accepted Paper
Spin-orbit-resolved resonant Auger spectrum of a dissociating HCl molecule
Phys. Rev. A - Accepted 1 October, 2026
DOI: https://doi.org/10.1103/ws2q-ky4n
Phys. Rev. A - Accepted 1 October, 2026
DOI: https://doi.org/10.1103/ws2q-ky4n
The photodissociation of HCl via the antibonding resonance occurs on the same 10-fs time scale as the Auger decay of the vacancy. This means that the and valence molecular orbitals involved in the electronic transition can significantly differ from the orbitals at the ground state equilibrium internuclear position. The non-relativistic resonant Auger (RA) spectrum based on the stationary Green’s function approach gives a good estimate of relative intensities of the three main spectral features in the eV emission energy range, but fails to reproduce highly resolved experimental data. We show that addition of the spin-orbit interaction of the and final states significantly improves the agreement for the spectral feature arising from the and states that converge to the H + Cl dissociation limit. Somewhat surprisingly, we found that the non-relativistic limit splits to five instead of three () dissociation limits of the Cl fragment at large internuclear distances. The similarity with the atomic case is broken because of a different nature of the molecular state, which is populated by a weak participator Auger decay and converges to a different, significantly higher H + Cl(P) dissociation limit. Our analysis shows that the remaining differences with an angle-integrated experimental spectrum are caused primarily by inaccuracies of the non-relativistic final state potentials and not by the one-center approximation of the spectator Auger transition rates. The potential slope differences are imprinted on the RA spectrum with a sensitivity and range depending on the duration of molecular dissociation with respect to the core-hole lifetime.
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