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ABINIT is a package whose main program allows one to find the total energy, charge density, electronic structure and many other properties of systems made of electrons and nuclei, (molecules and periodic solids) within Density Functional Theory (DFT), Many-Body Perturbation Theory (GW approximation and Bethe-Salpeter equation) and Dynmical Mean Field Theory (DMFT). ABINIT also allows to optimize the geometry according to the DFT forces and stresses, to perform molecular dynamics simulations using these forces, and to generate dynamical matrices, Born effective charges and dielectric tensors. The present paper aims to describe the new capabilities of ABINIT that have been developed since 2009. It covers both physical and technical developments inside the ABINIT code, as well as developments provided within the ABINIT package. The developments are described with relevant references, input variables, tests and tutorials.

We use a first-principles density functional theory approach to calculate the shift current and linear absorption of uniformly illuminated single-layer Ge and Sn monochalcogenides. We predict strong absorption in the visible spectrum and a large effective three-dimensional shift current (∼100 µA/V 2 ), larger than has been previously observed in other polar systems. Moreover, we show that the integral of the shift-current tensor is correlated to the large spontaneous effective threedimensional electric polarization (∼1.9 C/m 2 ). Our calculations indicate that the shift current will be largest in the visible spectrum, suggesting that these monochalcogenides may be promising for polar optoelectronic devices. A Rice-Mele tight-binding model is used to rationalize the shift-current response for these systems, and its dependence on polarization, in general terms with implications for other polar materials

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Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excitedstate properties relevant for optoelectronics applications. Predicting the structure and excited-state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) do not capture long-range vdW dispersion interactions and do not yield excited-state properties. In this work, we use a combination of DFT including vdW forces, using both nonlocal correlation functionals and pairwise correction methods, together with many-body perturbation theory (MBPT) to study the geometry and excited states, respectively, of the entire series of oligoacene crystals, from benzene to hexacene. We find that vdW methods can predict lattice constants within 1% of the experimental measurements, on par with the previously reported accuracy of pairwise approximations for the same systems. We further find that excitation energies are sensitive to geometry, but if optimized geometries are used MBPT can yield excited-state properties within a few tenths of an eV from experiment. We elucidate trends in MBPT-computed charged and neutral excitation energies across the acene series and discuss the role of common approximations used in MBPT.

Note: This article is part of the JCP Special Topic on Electronic Structure Software.

The accurate prediction of singlet and triplet excitation energies is an area of intense research of significant fundamental interest and critical for many applications. Most calculations of singlet and triplet energies use time-dependent density functional theory (TDDFT) in conjunction with an approximate exchange-correlation functional. In this work, we examine and critically assess an alternative method for predicting low-lying neutral excitations with similar computational cost, the ab initio Bethe-Salpeter equation (BSE) approach, and compare results against high-accuracy wavefunction-based methods. We consider singlet and triplet excitations of 27 prototypical organic molecules, including members of Thiel's set, the acene series, and several aromatic hydrocarbons exhibiting charge-transfer-like excitations. Analogous to its impact in TDDFT, we find that the Tamm-Dancoff approximation (TDA) overcomes triplet instabilities in the BSE approach, improving both triplet and singlet energetics relative to higher level theories. Finally, we find that BSE-TDA calculations built on effective DFT starting points, such as those utilizing optimally tuned range-separated hybrid functionals, can yield accurate singlet and triplet excitation energies for gas-phase organic molecules.

Charged excitations of the oligoacene family of molecules, relevant for astrophysics and technological applications, are widely studied and therefore provide an excellent system for benchmarking theoretical methods. In this work, we evaluate the performance of many-body perturbation theory (MPBT) within the GW approximation, relative to new high-quality CCSD(T) reference data, for charged excitations of the acenes. We compare GW calculations with a number of hybrid density functional theory starting points and with eigenvalue selfconsistency. Special focus is given to elucidating the trend of GW -predicted excitations with molecule length, from benzene to hexacene. We find that GW calculations with starting points based on an optimally-tuned range separated hybrid (OTRSH) density functional and eigenvalue self-consistency can yield quantitative ionization potentials for the acenes. However, for the larger acenes, the predicted electron affinities can deviate considerably from reference values. Our work paves the way for predictive and cost-effective GW calculations of chargedexcitations of molecules and identifies certain limitations of current GW methods used in practice for larger molecules.