Relativistic optimized effective potential method-application to alkali metals.

Area of Science:

• Computational Physics
• Quantum Chemistry
• Materials Science

Background:

• The accurate description of electronic structure is crucial for understanding material properties.
• Relativistic effects become significant for heavier elements and high-precision calculations.
• Existing methods may not efficiently treat both core and valence electrons within a unified relativistic framework.

Purpose of the Study:

• To present a relativistic formulation of the optimized effective potential (ROEP) method.
• To implement the ROEP method within the Korringa-Kohn-Rostoker (KKR) multiple scattering formalism.
• To apply this all-electron, relativistic approach to study non-magnetic alkali metals.

Main Methods:

• Developed a relativistic formulation of the optimized effective potential (ROEP) method.
• Employed the Korringa-Kohn-Rostoker (KKR) multiple scattering formalism for electronic structure calculations.
• Utilized numerical four-component wavefunctions and exact exchange (EXX) approximation for core and valence electrons.

Main Results:

• Successfully implemented a relativistic all-electron approach for electronic structure.
• Reformulated the exact exchange expression in terms of the electronic Green's function.
• Presented and discussed applications to non-magnetic alkali metals.

Conclusions:

• The developed relativistic ROEP-KKR method provides a robust all-electron approach.
• This formalism enables accurate treatment of relativistic effects for both core and valence states.
• The study demonstrates the applicability of the method to fundamental metallic systems.