Nuclear quantum effects made accessible: local-density fitting in multicomponent methods

Abstract The simulation of nuclear quantum effects (NQE) is crucial for an accurate description of systems and processes involving light nuclei such as hydrogen atoms. Within the last years, the importance of those effects has been highlighted for a vast range of systems with tremendous implications in chemistry, biology, physics and material sciences. However, while electronic structure theory methods have become routine tools for quantum chemical investigations, there is still a lack of approaches to address NQE which are as computationally accessible and straightforward to use. In an important step forward to change this scenario, we present the first combination of the Nuclear-Electronic Orbital Hartree-Fock approach with both local and density fitting approximations (LDF-NEO-HF). This results in a low-order scaling approach which enables the inclusion of nuclear quantum effects for large systems within a fraction of a day and for small to medium size systems in minutes. Moreover, we demonstrate the qualitative accuracy and robustness of our approach to retrieve NQEs for three real use cases motivated by chemical, biological and material science applications.