Periodic Constrained Nuclear-Electronic Orbital Density Functional Theory for Nuclear Quantum Effects: Method Development and Application to Hydrogen Adsorption on Pt(111)
Year: 2025
Type: article
Abstract: We develop constrained nuclear-electronic orbital density functional theory (CNEO-DFT) with periodic boundary conditions, enabling simultaneous quantum mechanical treatment of both electrons and nuclei in extended systems at computational costs comparable to conventional DFT. Our approach employs the Gaussian-augmented plane wave framework of CP2K for both electrons and nuclei. The quantum nuclei are treated as localized, distinguishable particles, while the collective nuclear distribution satisfies periodicity. When applied to hydrogen adsorption on Pt(111), our method predicts a shift in the preferred binding site from atop (conventional DFT) to fcc hollow (CNEO-DFT), primarily due to zero-point effects. Furthermore, by capturing subtle shallow tunneling effects that enhance hydrogen mobility, CNEO-DFT shows excellent agreement with fully quantum reference calculations for differential entropy across catalytically relevant temperatures (500-800 K). The implementation also includes analytic gradients, enabling geometry optimization and molecular dynamics. This development of periodic CNEO-DFT offers an accurate and efficient framework for treating nuclear quantum effects in surfaces, interfaces, and bulk materials where hydrogen chemistry plays a crucial role.
Authors: Zehua Chen, Yang Yang
Institution: University of Wisconsin–Madison
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G2032042173, G2567070707, Elements: Cyberinfrastructure for incorporating nuclear quantum effects in ab initio molecular simulations through constrained nuclear-electronic orbital density functional theory, CAREER: Development of Constrained Multicomponent Density Functional Theory and Accurate and Efficient Incorporation of Nuclear Quantum Effects in ab initio Molecular Dynamics
OpenAlex ID: W4413101338