Nuclear-Electronic Orbital Subsystem Density Functional Theory

Abstract

We present a new computational approach based on Nuclear-Electronic Orbital and Subsystem Density Functional Theory. The resulting NEO-sDFT methodology enables quantum chemical calculations of large molecular systems composed of thousands of atoms while also describing selected protons quantum mechanically. A key feature of the associated program implementation is its flexibility in assigning quantum protons to subsystems, allowing different embedding schemes to be employed within a unified framework. The accuracy of NEO-sDFT is assessed by computing water dimer interaction energies, which exhibit errors of only a few meV compared to reference Nuclear-Electronic Orbital Density Functional Theory results. The favorable computational scaling of NEO-sDFT is further showcased through calculations on water clusters of increasing size, with up to 303 protons being treated quantum mechanically. Our results demonstrate that NEO-sDFT is an accurate and efficient approach for incorporating nuclear quantum effects into large-scale simulations, providing a foundation for future applications to proton transfer processes in biochemical systems.