Toward Pair Atomic Density Fitting for Correlation Energies with Benchmark Accuracy.

Pair atomic density fitting (PADF) has been identified as a promising strategy to reduce the scaling with system size of quantum chemical methods for the calculation of the correlation energy like the direct random-phase approximation (RPA) or second-order Møller-Plesset perturbation theory (MP2). PADF can however introduce large errors in correlation energies as the two-electron interaction energy is not guaranteed to be bounded from below. This issue can be partially alleviated by using very large fit sets, but this comes at the price of reduced efficiency and having to deal with near-linear dependencies in the fit set. One posibility is to use global density fitting (DF), but in this work, we introduce an alternative methodology to overcome this problem that preserves the intrinsically favorable scaling of PADF. We first regularize the Fock matrix by projecting out parts of the basis set which gives rise to orbital products that are hard to describe by PADF. After having thus obtained a reliable self-consistent field solution, we then also apply this projector to the orbital coefficient matrix to improve the precision of PADF-MP2 and PADF-RPA. We systematically assess the accuracy of this new approach in a numerical atomic orbital framework using Slater type orbitals (STO) and correlation consistent Gaussian type basis sets up to quintuple-ζ quality for systems with more than 200 atoms. For the small and medium systems in the S66 database we show the maximum deviation of PADF-MP2 and PADF-RPA relative correlation energies to DF-MP2 and DF-RPA reference results to be 0.07 and 0.14 kcal/mol, respectively. When the new projector method is used, the errors only slightly increase for large molecules and also when moderately sized fit sets are used the resulting errors are well under control. Finally, we demonstrate the computational efficiency of our algorithm by calculating the interaction energies of large, non-covalently bound complexes with more than 1000 atoms and 20000 atomic orbitals at the RPA@PBE/CC-pVTZ level of theory.

Two-Dimensional Haeckelite NbS2 : A Diamagnetic High-Mobility Semiconductor with Nb4+ Ions.

In all known Group 5 transition-metal dichalcogenide monolayers (MLs), the metal centers carry a spin, and their ground-state phases are either metallic or semiconducting with indirect band gaps. Here, on grounds of first-principles calculations, we report that the Haeckelite polytypes 1S-NbX2 (X=S, Se, Te) are diamagnetic direct-band-gap semiconductors even though the Nb atoms are in the 4+ oxidation state. In contrast, 1S-VX2 MLs are antiferromagnetically coupled indirect-band-gap semiconductors. The 1S phases are thermodynamically and dynamically stable but of slightly higher energy than their 1H and 1T ML counterparts. 1S-NbX2 MLs are excellent candidates for optoelectronic applications owing to their small band gaps (between 0.5 and 1 eV). Moreover, 1S-NbS2 shows a particularly high hole mobility of 2.68×103  cm2 V-1 s-1 , which is significantly higher than that of MoS2 and comparable to that of WSe2 .

DFTB Parameters for the Periodic Table, Part 2: Energies and Energy Gradients from Hydrogen to Calcium.

In the first part of this series, we presented a parametrization strategy to obtain high-quality electronic band structures on the basis of density-functional-based tight-binding (DFTB) calculations and published a parameter set called QUASINANO2013.1. Here, we extend our parametrization effort to include the remaining terms that are needed to compute the total energy and its gradient, commonly referred to as repulsive potential. Instead of parametrizing these terms as a two-body potential, we calculate them explicitly from the DFTB analogues of the Kohn-Sham total energy expression. This strategy requires only two further numerical parameters per element. Thus, the atomic configuration and four real numbers per element are sufficient to define the DFTB model at this level of parametrization. The QUASINANO2015 parameter set allows the calculation of energy, structure, and electronic structure of all systems composed of elements ranging from H to Ca. Extensive benchmarks show that the overall accuracy of QUASINANO2015 is comparable to that of well-established methods, including PM7 and hand-tuned DFTB parameter sets, while coverage of a much larger range of chemical systems is available.

Electron transport in MoWSeS monolayers in the presence of an external electric field.

The influence of an external electric field on single-layer transition-metal dichalcogenides TX2 with T = Mo, W and X = S, Se (MoWSeS) has been investigated by means of density-functional theory within two-dimensional periodic boundary conditions under consideration of relativistic effects including the spin-orbit interactions. Our results show that the external field modifies the band structure of the monolayers, in particular, the conduction band. This modification has, however, very little influence on the band gap and effective masses of holes and electrons at the K point, and also the spin-orbit splitting of these monolayers is almost unaffected. Our results indicate a remarkable stability of the electronic properties of TX2 monolayers with respect to gate voltages. A reduction of the electronic band gap is observed starting only from field strengths of 2.0 V Å(-1) (3.5 V Å(-1)) for selenides (sulphides), and the transition to a metallic phase would occur at fields of 4.5 V Å(-1) (6.5 V Å(-1)).

DFTB Parameters for the Periodic Table: Part 1, Electronic Structure.

A parametrization scheme for the electronic part of the density-functional based tight-binding (DFTB) method that covers the periodic table is presented. A semiautomatic parametrization scheme has been developed that uses Kohn-Sham energies and band structure curvatures of real and fictitious homoatomic crystal structures as reference data. A confinement potential is used to tighten the Kohn-Sham orbitals, which includes two free parameters that are used to optimize the performance of the method. The method is tested on more than 100 systems and shows excellent overall performance.