Potential-functional embedding theory for molecules and materials.

Area of Science:

• Quantum Chemistry
• Computational Materials Science
• Theoretical Chemistry

Background:

• Density-functional embedding theory has been established for two decades.
• A recent density-based embedding theory was proposed.
• A dual problem to density-functional embedding theory was identified.

Purpose of the Study:

• Introduce a potential-functional embedding theory.
• Complete the dual problem in embedding theory.
• Provide a flexible and accurate computational framework for electronic structure calculations.

Main Methods:

• Reformulate density-based embedding theory using functionals of the embedding potential.
• Directly minimize the total energy functional to solve for the embedding potential.
• Derive gradients and forces for structural optimization and nuclear dynamics.
• Extend the theory to spin-polarized systems.

Main Results:

• The potential-functional formalism simplifies solving for the unique embedding potential.
• The theory accommodates charge transfer and fractional electrons.
• Different energy functionals can be used for different subsystems.
• Numerical examples demonstrate accuracy for molecules, chains, bulk materials, and surface adsorption.

Conclusions:

• The potential-functional embedding theory offers a robust and versatile approach.
• It enables efficient and accurate calculations for complex chemical systems.
• The framework supports structural optimization and dynamic simulations.