Periodic Constrained Nuclear-Electronic Orbital Density Functional Theory for Nuclear Quantum Effects: Method Development and Application to Hydrogen Adsorption on Pt(111).

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 mob

SUBMITTER: Chen Z 

PROVIDER: S-EPMC12503368 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature