Nuclear-electronic orbital methods: Foundations and prospects.

Abstract

The incorporation of nuclear quantum effects and non-Born-Oppenheimer behavior into quantum chemistry calculations and molecular dynamics simulations is a longstanding challenge. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons, quantum mechanically on the same level as the electrons with wave function and density functional theory methods. This approach inherently includes nuclear delocalization and zero-point energy in molecular energy calculations, geometry optimizations, reaction paths, and dynamics. It can also provide accurate descriptions of excited electronic, vibrational, and vibronic states as well as nuclear tunneling and nonadiabatic dynamics. Nonequilibrium nuclear-electronic dynamics simulations beyond the Born-Oppenheimer approximation can be used to investigate a wide range of excited state processes. This Perspective provides an overview of the foundational NEO methods and enumerates the prospects for using these methods as building blocks for future developments. The conceptual simplicity and computational efficiency of the NEO approach will enhance its accessibility and applicability to diverse chemical and biological systems.