| Autor: |
Xu J; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA., Zhou R; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA., Tao Z; Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Malbon C; Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Blum V; Thomas Lord Department of Mechanical Engineering and Material Science, Duke University, Durham, North Carolina 27708, USA., Hammes-Schiffer S; Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA., Kanai Y; Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA. |
| Abstrakt: |
The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the NEO method for periodic electronic structure calculations, particularly focused on multicomponent density functional theory (DFT). The NEO-DFT method is implemented in an all-electron electronic structure code, FHI-aims, using a combination of analytical and numerical integration techniques as well as a resolution of the identity scheme to enhance computational efficiency. After validating this implementation, proof-of-concept applications are presented to illustrate the effects of quantized protons on the physical properties of extended systems, such as two-dimensional materials and liquid-semiconductor interfaces. Specifically, periodic NEO-DFT calculations are performed for a trans-polyacetylene chain, a hydrogen boride sheet, and a titanium oxide-water interface. The zero-point energy effects of the protons as well as electron-proton correlation are shown to noticeably impact the density of states and band structures for these systems. These developments provide a foundation for the application of multicomponent DFT to a wide range of other extended condensed matter systems. |
