Ionization satellites of the ArHe dimer

Area of Science:

• Atomic and Molecular Physics
• Quantum Chemistry
• Chemical Physics

Background:

• Ionization satellites are crucial for understanding post-ionization dynamics like molecular dissociation and interatomic Coulombic decay.
• Previous models often describe satellites as a Rydberg electron interacting with a dicationic core, a concept applied to alkaline earth metal and rare gas complexes.

Purpose of the Study:

• To investigate the potential energy curves (PECs) of ionization satellites in the ArHe dimer.
• To assess the validity of the simple Rydberg electron-dicationic core model for rare gas clusters.

Main Methods:

• Employed a high-level ab initio multi-reference configuration interaction method, including triple excitations.
• Calculated and analyzed the potential energy curves (PECs) for the ArHe dimer's ionization satellites.

Main Results:

• Demonstrated that the simple model does not fully apply to rare gas clusters like ArHe.
• Observed significant mixing of electronic configurations due to the complex valence structure of rare gas atoms.
• Identified cases where a single dicationic parent state cannot be assigned to ionization satellites.
• Analyzed PEC structures, correlating them with Rydberg electron density where the simple model remains applicable.

Conclusions:

• The electronic complexity of rare gas atoms necessitates a more sophisticated model than the simple Rydberg electron-dicationic core approach for describing ionization satellites.
• Potential energy curve analysis provides insights into electron density distributions and the limitations of simplified models in ArHe systems.