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Nuclear–electronic orbital approach to quantization of protons in periodic electronic structure calculations


Nuclear–electronic orbital approach to quantization of protons in periodic electronic structure calculations

Abstract

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.



Citation

Xu J, Zhou R, Tao Z, Malbon C, Blum V, Hammes-Schiffer S, Kanai Y. Nuclear-electronic orbital approach to quantization of protons in periodic electronic structure calculations. J Chem Phys. 2022 Jun 14;156(22):224111. doi: 10.1063/5.0088427. PMID: 35705422.


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