Toward Chemical Accuracy for Chemi- and Physisorption with an Efficient Density Functional.

Area of Science:

• Surface Science
• Computational Chemistry
• Materials Science

Background:

• Molecular adsorption on surfaces is critical in chemistry and materials science.
• First-principles methods face challenges in accurately describing both chemical and physical adsorption, including van der Waals (vdW) interactions.
• Existing density functional approximations often struggle to capture both types of adsorption accurately.

Purpose of the Study:

• To develop an efficient and accurate density functional approximation for molecular adsorption.
• To address limitations in current methods for describing combined chemical and physical adsorption.
• To enable reliable first-principles modeling of adsorption processes.

Main Methods:

• Developed a novel density functional approximation by concurrently optimizing its semilocal component and long-range vdW correction.
• Validated the method against the prototypical CO/Pt(111) adsorption system.
• Tested the approach using the Ar2 binding energy curve.

Main Results:

• The proposed density functional approximation demonstrates accuracy for both chemical and physical adsorption.
• The method effectively captures the interplay between short-range chemical bonding and long-range vdW interactions.
• Optimized parameters provide reliable predictions for adsorption energies and interactions.

Conclusions:

• The new density functional approximation offers an accurate and efficient tool for modeling molecular adsorption.
• This advancement facilitates better understanding and design in surface chemistry and materials science.
• The method paves the way for broader applications in predicting adsorption phenomena.