Search

We present the implementation of the Hubbard ($U$) and Hund ($J$) corrected Density Functional Theory (DFT+$U$+$J$) functionality in the Quickstep program, which is part of the CP2K suite. The tensorial and L\"owdin subspace representations are implemented and compared. Full analytical DFT+$U$+$J$ forces are implemented and benchmarked for the tensorial and L\"owdin representations. We also present the implementation of the recently proposed minimum-tracking linear-response method that enables the $U$ and $J$ parameters to be calculated on first principles basis without reference to the Kohn-Sham eigensystem. These implementations are benchmarked against recent results for different materials properties including DFT+$U$ band gap opening in NiO, the relative stability of various polaron distributions in TiO$_2$, the dependence of the calculated TiO$_2$ band gap on +$J$ corrections, and, finally, the role of the +$U$ and +$J$ corrections for the computed properties of a series of the hexahydrated transition metals. Our implementation provides results consistent with those already reported in the literature from comparable methods. We conclude the contribution with tests on the influence of the L\"owdin orthonormalization on the occupancies, calculated parameters, and derived properties.

FAPbI3, as a typical hybrid organic-inorganic perovskite, has attracted considerable interest due to its band gap suitable for visible light absorption and good thermal stability. A barrier to the use of FAPbI3 in commercial, stable devices is its unwanted black-to-yellow (non-perovskite to perovskite, commonly known as delta-to-alpha) phase transition at around 300 K. The intrinsic mechanisms of such phase transition are far from clear, being the detailed structural description for the alpha-phase still missing. By combined Density Functional Theory (DFT) calculations, lattice dynamics analysis and DFT molecular dynamics simulations, we assign the alpha-phase to the highly dynamic tetragonal phase, with the high-symmetry cubic structure emerging as a dynamically unstable maximum in the system potential energy landscape. We demonstrate computationally that the diffraction-observed cubic structure is the result of the averaging of different tetragonal distortions sampled in the experimental detection time scale as a result of the enhanced FA dynamics, instead of a static system of cubic symmetry. Further finite-temperature Gibbs free energy calculations confirm that the delta-to-alpha transition should be considered as a hexagonal-to-tetragonal transition in contrast to the previous hexagonal-to-cubic assignment. More importantly, the simulations indicate that the driving force of the process is the vibrational entropy difference rather than the rotational entropy as previously proposed. These results point out the dynamical nature of the alpha-phase, the importance of the overlooked tetragonal structure, and the key role of the vibrational entropy in perovskite-related phase transitions, the harnessing of which is critical for successful uptake of ABX3 hybrid organic-inorganic perovskites in commercial applications.

The topological edge states of two-dimensional topological insulators with large energy gap furnish ideal conduction channels for dissipationless current transport. Transition metal tellurides XTe5 (X=Zr, Hf) are theoretically predicted to be large-gap two-dimensional topological insulators and the experimental observations of their bulk insulating gap and in-gap edge states have been reported, but the topological nature of these edge states still remains to be further elucidated. Here, we report our low temperature scanning tunneling microscopy/spectroscopy study on single crystals of HfTe5. We demonstrate a full energy gap of ~80 meV near the Fermi level on the surface monolayer of HfTe5 and that such insulating energy gap gets filled with finite energy states when measured at the monolayer step edges. Remarkably, such states are absent at the edges of a narrow monolayer strip of one-unit-cell in width but persist at both step edges of a unit-cell wide monolayer groove. These experimental observations strongly indicate that the edge states of HfTe5 monolayers are not trivially caused by translational symmetry breaking, instead they are topological in nature protected by the 2D nontrivial bulk properties.

The atomic structure, stacking sequences and electronic structure of folded graphene nanoribbons (FGNRs) are investigated by first-principles calculations. It reveals that the common configurations of all FGNRs are racket-like structures including a nanotube-like edge and two flat nanoribbons. Interestingly, the two flat nanoribbons can form new stacking styles instead of the most stable AB-stacking sequences for bilayer nanoribbons. The stability of the FGNRs are associated with several factors of initial structures, such as interlayer distance of two nanoribbons, stacking sequences, edge styles, and width of nanoribbons. These folded nanoribbons can only be thermodynamically stable when the width reaches about 61 {\AA} and 95 {\AA} for the zigzag and armchair nanoribbons, respectively. In addition, the band gap of the folded zigzag graphene nanoribbons becomes about 0.17 eV, which provides a new way to open the band gap.

A novel two-dimensional carbon allotrope, rectangular graphyne (R-graphyne) with tetra-rings and acetylenic linkages, is proposed by first-principles calculations. Although the bulk R-graphyne exhibits metallic property, the nanoribbons of R-graphyne show distinct electronic structures from the bulk. The most intriguing feature is that band gaps of R-graphene nanoribbons oscillate between semiconductor and metal as a function of width. Particularly, the zigzag edge nanoribbons with half-integer repeating unit cell exhibits unexpected Dirac-like fermions in the band structures. The Dirac-like fermions of the R-graphyne nanoribbons originate from the central symmetry and two sub-lattices. The extraordinary properties of R-graphene nanoribbons greatly expand our understanding on the origin of Dirac-like point. Such findings uncover a novel fascinating property of nanoribbons, which may have broad potential applications for carbon-based nano-size electronic devices.

Graphite may be viewed as a low-surface-energy carbon allotrope with little layer-layer interaction. Other low-surface-energy allotropes but with much stronger layer-layer interaction may also exist. Here, we report a first-principles prediction for one of the known carbon allotropes, bcc-C6 (a body centered carbon allotrope with six atoms per primitive unit) that should have exceptionally low-surface energy and little size dependence down to only a couple layer thickness. This unique property may explain the existence of the relatively-high-energy bcc-C6 during growth. The electronic properties of the bcc-C6thin layers can also be intriguing: the (111), (110), and (001) thin layers havedirect band gap, indirect band gap, and metallic character, respectively. The refrained chemical reactivity of the thin layers does not disappear after cleaving, as lithium-doped (Li-doped) 3-layers (111) has a noticeably increased binding energies of H2 molecules with a maximum storage capacity of 10.8 wt%.

Three single-layer tetragonal silicon carbides (SiC), termed as T1,T2 and T3, are proposed by density functional theory (DFT) computations. Although the three structures have the same topological geometry, they show versatile electronic properties from semiconductor (T1), semimetal (T2) to metal (T3).The versatile properties are originated from the rich bonds between Si and C atoms. The nanoribbons of the three SiC also show interesting electronic properties. Especially, T1 nanoribbons possess exotic edge states, where electrons only distribute on one edge's silicon or carbon atoms. The band gaps of the T1 nanoribbons are constant because of no interaction between the edge states.