Light--absorbed orbital angular momentum in the linear response regime

In exploring the light-induced dynamics within the linear response regime, this study investigates the induced orbital angular momentum on a wide variety of electronic structures. We derive a general expression for the torque induced by light on different electronic systems based on their characteristic dielectric tensor. We demonstrate that this phenomenon diverges from the inverse Faraday effect as it produces an orbital magnetization persistent post-illumination. Indeed, our results reveal that, while isotropic non-dissipative materials do not absorb orbital angular momentum from circularly polarized light, any symmetry-breaking arrangement of matter, be it spatial or temporal, introduces novel channels for the absorption of orbital angular momentum, or magnetization. Most notably, in dissipative materials, circularly polarized light imparts a torque corresponding to a change in orbital angular momentum of $\hbar$ per absorbed photon. The potential of these mechanisms to drive helicity-dependent magnetic phenomena paves the way for a deeper understanding of light-matter interactions. Notably, the application of pump-probe techniques in tandem with our findings allows experimentalists to quantitatively assess the amount of orbital angular momentum transferred to electrons in matter, thus hopefully enhancing our ability to steer ultrafast light-induced magnetization dynamics

Adsorption of Cu, Ag, and Au atoms on graphene including van der Waals interactions

We performed a systematic density functional study of the adsorption of copper, silver, and gold adatoms on graphene, especially accounting for van der Waals interactions by the vdW-DF and the PBE+D2 methods. In particular, we analyze the preferred adsorption site (among top, bridge, and hollow positions) together with the corresponding distortion of the graphene sheet and identify diffusion paths. Both vdW schemes show that the coinage metal atoms do bind to the graphene sheet and that in some cases the buckling of the graphene can be significant. The results for silver are at variance with those obtained with GGA, which gives no binding in this case. However, we observe some quantitative differences between the vdW-DF and the PBE+D2 methods. For instance the adsorption energies calculated with the PBE+D2 method are systematically higher than the ones obtained with vdW-DF. Moreover, the equilibrium distances computed with PBE+D2 are shorter than those calculated with the vdW-DF method

Hybrid localized graph kernel for machine learning energy-related properties of molecules and solids

Nowadays, the coupling of electronic structure and machine learning techniques serves as a powerful tool to predict chemical and physical properties of a broad range of systems. With the aim of improving the accuracy of predictions, a large number of representations for molecules and solids for machine learning applications has been developed. In this work we propose a novel descriptor based on the notion of molecular graph. While graphs are largely employed in classification problems in cheminformatics or bioinformatics, they are not often used in regression problem, especially of energy-related properties. Our method is based on a local decomposition of atomic environments and on the hybridization of two kernel functions: a graph kernel contribution that describes the chemical pattern and a Coulomb label contribution that 1encodes finer details of the local geometry. The accuracy of this new kernel method in energy predictions of molecular and condensed phase systems is demonstrated by considering the popular QM7 and BA10 datasets. These examples show that the hybrid localized graph kernel outperforms traditional approaches such as, for example, the smooth overlap of atomic positions (SOAP) and the Coulomb matrices

Electronic Structure and Band Alignments of Various Phases of Titania Using the Self-Consistent Hybrid Density Functional and DFT+U Methods

To understand, and thereby rationally optimize photoactive interfaces, it is of great importance to elucidate the electronic structures and band alignments of these interfaces. For the first-principles investigation of these properties, conventional density functional theory (DFT) requires a solution to mitigate its well-known bandgap underestimation problem. Hybrid functional and Hubbard U correction are computationally efficient methods to overcome this limitation, however, the results are largely dependent on the choice of parameters. In this study, we employed recently developed self-consistent approaches, which enable non-empirical determination of the parameters, to investigate TiO2 interfacial systems—the most prototypical photocatalytic systems. We investigated the structural, electronic, and optical properties of rutile and anatase phases of TiO2. We found that the self-consistent hybrid functional method predicts the most reliable structural and electronic properties that are comparable to the experimental and high-level GW results. Using the validated self-consistent hybrid functional method, we further investigated the band edge positions between rutile and anatase surfaces in a vacuum and electrolyte medium, by coupling it with the Poisson-Boltzmann theory. This suggests the possibility of a transition from the straddling-type to the staggered-type band alignment between rutile and anatase phases in the electrolyte medium, manifested by the formation of a Stern-like layer at the interfaces. Our study not only confirms the efficacy of the self-consistent hybrid functional method by reliably predicting the electronic structure of photoactive interfaces, but also elucidates a potentially dramatic change in the band edge positions of TiO2 in aqueous electrolyte medium which can extensively affect its photophysical properties

Assessing the Performance of Recent Density Functionals for Bulk Solids

We assess the performance of recent density functionals for the exchange-correlation energy of a nonmolecular solid, by applying accurate calculations with the GAUSSIAN, BAND, and VASP codes to a test set of 24 solid metals and non-metals. The functionals tested are the modified Perdew-Burke-Ernzerhof generalized gradient approximation (PBEsol GGA), the second-order GGA (SOGGA), and the Armiento-Mattsson 2005 (AM05) GGA. For completeness, we also test more-standard functionals: the local density approximation, the original PBE GGA, and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA. We find that the recent density functionals for solids reach a high accuracy for bulk properties (lattice constant and bulk modulus). For the cohesive energy, PBE is better than PBEsol overall, as expected, but PBEsol is actually better for the alkali metals and alkali halides. For fair comparison of calculated and experimental results, we consider the zero-point phonon and finite-temperature effects ignored by many workers. We show how Gaussian basis sets and inaccurate experimental reference data may affect the rating of the quality of the functionals. The results show that PBEsol and AM05 perform somewhat differently from each other for alkali metal, alkaline earth metal and alkali halide crystals (where the maximum value of the reduced density gradient is about 2), but perform very similarly for most of the other solids (where it is often about 1). Our explanation for this is consistent with the importance of exchange-correlation nonlocality in regions of core-valence overlap.Comment: 32 pages, single pdf fil

Advances in Density-Functional Calculations for Materials Modeling

During the past two decades, density-functional (DF) theory has evolved from niche applications for simple solid-state materials to become a workhorse method for studying a wide range of phenomena in a variety of system classes throughout physics, chemistry, biology, and materials science. Here, we review the recent advances in DF calculations for materials modeling, giving a classification of modern DF-based methods when viewed from the materials modeling perspective. While progress has been very substantial, many challenges remain on the way to achieving consensus on a set of universally applicable DF-based methods for materials modeling. Hence, we focus on recent successes and remaining challenges in DF calculations for modeling hard solids, molecular and biological matter, low-dimensional materials, and hybrid organic-inorganic materials

Crystal and electronic structures of nitridophosphate compounds as cathode materials for Na-ion batteries

International audienceUsing density-functional theory, we have studied the electronic and magnetic properties of two promising compounds that can be used as cathode materials, namely, Na2Fe2P3O9N and Na-3 TiP3O9N. When Na is extracted, we found the volume change to be quite small, with values of similar to-0.6% for Na3TiP3O9N and -5% for Na2Fe2P3O9N. Our calculated voltageswith theHubbard-type correction (GGA+U) approximation are 2.93 V for Na3TiP3O9N/Na2TiP3O9N and 2.68 V for Na2Fe2P3O9N/NaFe2P3O9N, in good agreement with the experimental data. Our results confirm that these compounds are very promising for rechargeable Na-ion batteries

Dispersion Corrected Structural Properties and Quasiparticle Band Gaps of Several Organic Energetic Solids

International audienceWe have performed ab initio calculations for a series of energetic solids to explore their structural and electronic properties. To evaluate the ground state Volume of these molecular solids, different dispersion correct on methods were accounted in DFT, namely the Tkatchenko-Scheffler method (With and without self-consistent screening), Grimme's methods D2, D3(BJ)), and the vdW-DF method. Our results reveal that dispersion correction methods are essential it understanding these complex structures with van der Waals interactions and hydrogen bonding. The calculated ground state volumes and bulk moduli show that the performance of each method is not unique, and therefore a careful examination is mandatory for interpreting theoretical predictions. This work also emphasizes the importance of quasiparticle calculations in predicting the band gap, which is obtained here with the GW approximation. We find that the obtained band gaps are ranging froth 4 to 7 eV for the different compounds, indicating their insulating nature. In addition, we show the essential role of quasiparticle band structure calculations to correlate the gap with the energetic properties