Introducing a dielectric bath embedding theory for embedded electronic structure calculations in heterogeneous...

Area of Science:

• Computational Chemistry
• Materials Science
• Surface Science

Background:

• Accurate modeling of reactions on metallic surfaces is crucial but challenging for electronic structure theories.
• Density functional theory (DFT) often provides inaccurate descriptions of electronic structures and reaction kinetics.
• Correlated wavefunction (CW) theories offer higher accuracy but are computationally expensive for large systems.

Purpose of the Study:

• To develop a more efficient and accurate quantum embedding theory for modeling metallic surface reactions.
• To reduce the computational cost associated with traditional density functional embedding theory (DFET) methods.
• To improve the prediction of electronic properties and adsorbate interactions on metal surfaces.

Main Methods:

• Introduction of a novel polarizable embedding scheme combining an external local potential with a dielectric bath.
• Replacement of the computationally intensive optimized effective potential process in DFET with a physics-informed approach.
• Validation of the scheme using the Cu(111) surface with multiple adsorbates.

Main Results:

• The proposed polarizable embedding scheme significantly reduces computational cost compared to standard DFET.
• The new approach demonstrates superior performance in predicting the Fermi level, charge states, and binding strengths.
• Outperforms standard DFET in accurately describing the electronic properties and interactions of adsorbates on Cu(111).

Conclusions:

• The developed polarizable embedding scheme offers a more efficient and robust alternative for correlated wavefunction calculations.
• This method has the potential to accelerate the adoption of advanced electronic structure theories in heterogeneous catalysis.
• Enables more accurate and cost-effective simulations of surface reactions relevant to catalysis.