Communication: electron transfer mediated decay enabled by spin-orbit interaction in small krypton/xenon clusters.

Area of Science:

• Atomic and Molecular Physics
• Quantum Chemistry
• Relativistic Quantum Mechanics

Background:

• Electronic decay processes in clusters are crucial for understanding molecular fragmentation.
• Relativistic effects, such as spin-orbit coupling, are known to influence electronic structure and dynamics, especially in systems with heavy elements.
• The interplay between cluster geometry and relativistic effects on decay pathways remains an area requiring further investigation.

Purpose of the Study:

• To investigate the influence of relativistic effects, particularly spin-orbit coupling, on electronic decay processes in Krypton-Xenon (KrXe2) clusters.
• To determine if spin-orbit coupling affects the accessibility of specific electronic decay pathways in these clusters.
• To explore the dependence of competing electronic decay pathways on cluster geometry and theoretical level.

Main Methods:

• Utilized a fully relativistic theoretical framework for electronic structure calculations.
• Simulated electronic decay processes initiated by Krypton 4s ionization.
• Modeled subsequent electron transfer from Xenon to Krypton and a second ionization event.

Main Results:

• Demonstrated that spin-orbit coupling has a decisive influence on the accessibility of specific electronic decay pathways in KrXe2 clusters.
• Identified competing electronic decay pathways that are subtly dependent on cluster geometry and the level of theoretical treatment.
• Showed that omitting spin-orbit coupling in calculations leads to the closure of two potential decay pathways.

Conclusions:

• The inclusion of spin-orbit coupling is essential for an accurate description of electronic decay dynamics in KrXe2 clusters.
• Relativistic effects play a critical role in determining fragmentation dynamics, especially for clusters containing heavy elements like Krypton and Xenon.
• These findings underscore the importance of employing adequate relativistic theoretical methods when studying heavy element systems.