Hybridization and coherence in subshell differential intercluster plasmonic decay in Na20@C240.

Area of Science:

• Physical Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Endohedral fullerenes encapsulate atoms or clusters within fullerene cages.
• The electronic structure of these systems is influenced by the interaction between the guest and host.
• Understanding photoionization dynamics is crucial for potential applications.

Purpose of the Study:

• Investigate the ground state structure of Na20@C240.
• Analyze the photoionization dynamics influenced by electronic coupling.
• Elucidate the mechanisms behind enhanced ionization yields.

Main Methods:

• Density Functional Theory (DFT) calculations.
• Jellium model for fullerene electronic structure.
• Analysis of electronic coupling, electron transfer, and hybridization.
• Study of photoionization cross-sections and plasmon decay dynamics.

Main Results:

• Observed electronic coupling leads to potential alterations, electron transfer, and hybridization.
• Significant enhancement in photoionization cross-section for Na20-type levels due to C240.
• Photoexcited plasmons in C240 decay via resonant intercluster Coulombic decay (ICD) into the Na20 ionization continuum.
• Dramatic enhancement in Na20 ionization yield due to ICD and SAMO-induced Auger decay.

Conclusions:

• Electronic coupling profoundly modifies the Na20@C240 system's properties.
• Intercluster Coulombic decay (ICD) is a dominant mechanism for enhanced ionization.
• Hybridization of electronic states plays a key role in the observed phenomena.