Nuclear-Electronic Orbital Multistate Density Functional Theory.

Abstract

Hydrogen tunneling is essential for a wide range of chemical and biological processes. The description of hydrogen tunneling with multicomponent quantum chemistry approaches, where the transferring hydrogen nucleus is treated on the same level as the electrons, is challenging due to the importance of both static and dynamical electron-proton correlation. Herein the nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method is presented as a strategy to include both types of correlation. In this approach, two localized nuclear-electronic wave functions obtained with the NEO-DFT method are combined with a nonorthogonal configurational interaction approach to produce bilobal, delocalized ground and excited vibronic states. By including a correction function, the NEO-MSDFT approach can produce quantitatively accurate hydrogen tunneling splittings for fixed geometries of systems such as malonaldehyde and acetoacetaldehyde. This approach is computationally efficient and can be combined with methods such as vibronic coupling theory to describe tunneling dynamics and to compute vibronic couplings in many types of systems.