Density functional theory beyond the Born-Oppenheimer approximation: accurate treatment of the ionic zero-point motion

Abstract

We introduce a method to carry out zero-temperature calculations within density functional theory (DFT) but without relying on the Born-Oppenheimer (BO) approximation for the ionic motion. Our approach is based on the finite-temperature many-body path-integral formulation of quantum mechanics by taking the zero-temperature limit and treating the imaginary-time propagation of the electronic variables in the context of DFT. This goes beyond the familiar BO approximation and is limited from being an exact treatment of both electrons and ions only by the approximations involved in the DFT component. We test our method in two simple molecules, H${}_2$ and benzene. We demonstrate that the method produces a difference from the results of the BO approximation which is significant for many physical systems, especially those containing light atoms such as hydrogen; in these cases, we find that the fluctuations of the distance from its equilibrium position, due to the zero-point-motion, is comparable to the interatomic distances. The method is suitable for use with conventional condensed matter approaches and currently is implemented on top of the periodic pseudopotential code SIESTA.

arXiv commentThis version contains some corrections and clarifications

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Cited by in corpus (3)

• Two-component density functional theory for muonic molecules: Inclusion of the electron-positive muon correlation functional
• Imaginary-time time-dependent density functional theory and its application for robust convergence of electronic states
• Quantifying errors of the electron-proton/muon correlation functionals through the Kohn-Sham inversion of a two-component model system