• Accepted Paper

Spin-orbit-resolved resonant Auger spectrum of a dissociating HCl molecule

M. Žitnik, J. Turnšek, K. Bučar, and A. Mihelič

Phys. Rev. A - Accepted 1 October, 2026

DOI: https://doi.org/10.1103/ws2q-ky4n

Abstract

The photodissociation of HCl via the antibonding 2p−1σ* resonance occurs on the same 10-fs time scale as the Auger decay of the 2p vacancy. This means that the v,v′ and σ* valence molecular orbitals involved in the electronic transition can significantly differ from the orbitals at the ground state equilibrium internuclear position. The non-relativistic L−vv′ 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 173−182 eV emission energy range, but fails to reproduce highly resolved experimental data. We show that addition of the spin-orbit interaction of the 2π−2σ* and 5σ−12π−1σ* final states significantly improves the agreement for the spectral feature arising from the 4Π,2Σ and 4Σ states that converge to the H + Cl+(3P) dissociation limit. Somewhat surprisingly, we found that the 3P non-relativistic limit splits to five instead of three 3p−2(3P0,1,2) 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 2Π molecular state, which is populated by a weak participator Auger decay and converges to a different, significantly higher H+ + Cl(2P) 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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