Real-time nuclear-electronic orbital time-dependent density functional theory with a constrained traveling proton...

Nuclear quantum effects and non-Born-Oppenheimer effects play a vital role in many chemical and biological processes, motivating the incorporation of such effects into dynamical simulations. In real-time nuclear-electronic orbital time-dependent density functional theory (RT-NEO-TDDFT), the electronic and nuclear densities are propagated numerically in time according to the time-dependent Schrödinger equation. In this framework, specified protons are treated quantum mechanically on the same level as the electrons. The classical nuclei can be propagated on the instantaneous NEO vibronic surface using Ehrenfest dynamics. A traveling proton basis (TPB) can be used to describe the dynamics of moving protons in conjunction with Gaussian-type protonic and electronic basis sets for each quantum proton. Herein, we present a constrained TPB (c-TPB) approach that ensures each protonic basis function center coincides with the corresponding proton position expectation value during the dynamics. This approach produces accurate nuclear-electronic quantum dynamics and rigorously conserves energy. We demonstrate the accuracy and stability of this approach for computing molecular vibrational frequencies as well as simulating excited-state intramolecular proton transfer and double proton transfer in the o-hydroxybenzaldehyde and [2,2'-bipyridyl]-3,3'-diol molecules. These applications show that the c-TPB method provides accurate dynamics, conserves energy, and is computationally efficient.