GPAW: An open Python package for electronic structure calculations.

We review the GPAW open-source Python package for electronic structure calculations. GPAW is based on the projector-augmented wave method and can solve the self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, and numerical atomic orbitals. The three representations are complementary and mutually independent and can be connected by transformations via the real-space grid. This multi-basis feature renders GPAW highly versatile and unique among similar codes. By virtue of its modular structure, the GPAW code constitutes an ideal platform for the implementation of new features and methodologies. Moreover, it is well integrated with the Atomic Simulation Environment (ASE), providing a flexible and dynamic user interface. In addition to ground-state DFT calculations, GPAW supports many-body GW band structures, optical excitations from the Bethe-Salpeter Equation, variational calculations of excited states in molecules and solids via direct optimization, and real-time propagation of the Kohn-Sham equations within time-dependent DFT. A range of more advanced methods to describe magnetic excitations and non-collinear magnetism in solids are also now available. In addition, GPAW can calculate non-linear optical tensors of solids, charged crystal point defects, and much more. Recently, support for graphics processing unit (GPU) acceleration has been achieved with minor modifications to the GPAW code thanks to the CuPy library. We end the review with an outlook, describing some future plans for GPAW.

Chemical bonding theories as guides for self-interaction corrected solutions: Multiple local minima and symmetry breaking.

Fermi-Löwdin orbitals (FLOs) are a special set of localized orbitals, which have become commonly used in combination with the Perdew-Zunger self-interaction correction (SIC) in the FLO-SIC method. The FLOs are obtained for a set of occupied orbitals by specifying a classical position for each electron. These positions are known as Fermi-orbital descriptors (FODs), and they have a clear relation to chemical bonding. In this study, we show how FLOs and FODs can be used to initialize, interpret, and justify SIC solutions in a common chemical picture, both within FLO-SIC and in traditional variational SIC, and to locate distinct local minima in either of these approaches. We demonstrate that FLOs based on Lewis theory lead to symmetry breaking for benzene-the electron density is found to break symmetry already at the symmetric molecular structure-while ones from Linnett's double-quartet theory reproduce symmetric electron densities and molecular geometries. Introducing a benchmark set of 16 planar cyclic molecules, we show that using Lewis theory as the starting point can lead to artifactual dipole moments of up to 1 D, while Linnett SIC dipole moments are in better agreement with experimental values. We suggest using the dipole moment as a diagnostic of symmetry breaking in SIC and monitoring it in all SIC calculations. We show that Linnett structures can often be seen as superpositions of Lewis structures and propose Linnett structures as a simple way to describe aromatic systems in SIC with reduced symmetry breaking. The role of hovering FODs is also briefly discussed.

Variational calculations of excited states via direct optimization of the orbitals in DFT.

A direct optimization method for obtaining excited electronic states using density functionals is presented. It involves selective convergence on saddle points on the energy surface representing the variation of the energy as a function of the electronic degrees of freedom, thereby avoiding convergence to a minimum and corresponding variational collapse to the ground electronic state. The method is based on an exponential transformation of the molecular orbitals, making it possible to use efficient quasi-Newton optimization approaches. Direct convergence on a target nth-order saddle point is guided by an appropriate preconditioner for the optimization as well as the maximum overlap method. Results of benchmark calculations of 52 excited states of molecules indicate that the method is more robust than a standard self-consistent field (SCF) approach especially when degenerate or quasi-degenerate orbitals are involved. The method can overcome challenges arising from rearrangement of closely spaced orbitals in a charge-transfer excitation of the nitrobenzene molecule, a case where the SCF fails to converge. The formulation of the method is general and can be applied to non-unitary invariant functionals, such as self-interaction corrected functionals.

Measuring Electron Correlation: The Impact of Symmetry and Orbital Transformations.

In this perspective, the various measures of electron correlation used in wave function theory, density functional theory and quantum information theory are briefly reviewed. We then focus on a more traditional metric based on dominant weights in the full configuration solution and discuss its behavior with respect to the choice of the N-electron and the one-electron basis. The impact of symmetry is discussed, and we emphasize that the distinction among determinants, configuration state functions and configurations as reference functions is useful because the latter incorporate spin-coupling into the reference and should thus reduce the complexity of the wave function expansion. The corresponding notions of single determinant, single spin-coupling and single configuration wave functions are discussed and the effect of orbital rotations on the multireference character is reviewed by analyzing a simple model system. In molecular systems, the extent of correlation effects should be limited by finite system size and in most cases the appropriate choices of one-electron and N-electron bases should be able to incorporate these into a low-complexity reference function, often a single configurational one.

Variational Density Functional Calculations of Excited States: Conical Intersection and Avoided Crossing in Ethylene Bond Twisting.

Theoretical studies of photochemical processes require a description of the energy surfaces of excited electronic states, especially near degeneracies, where transitions between states are most likely. Systems relevant to photochemical applications are typically too large for high-level multireference methods, and while time-dependent density functional theory (TDDFT) is efficient, it can fail to provide the required accuracy. A variational, time-independent density functional approach is applied to the twisting of the double bond and pyramidal distortion in ethylene, the quintessential model for photochemical studies. By allowing for symmetry breaking, the calculated energy surfaces exhibit the correct topology around the twisted-pyramidalized conical intersection even when using a semilocal functional approximation, and by including explicit self-interaction correction, the torsional energy curves are in close agreement with published multireference results. The findings of the present work point to the possibility of using a single determinant time-independent density functional approach to simulate nonadiabatic dynamics, even for large systems where multireference methods are impractical and TDDFT is often not accurate enough.

Method for Calculating Excited Electronic States Using Density Functionals and Direct Orbital Optimization with Real Space Grid or Plane-Wave Basis Set.

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane-wave basis set. The method is variational, provides atomic forces in the excited states, and can be applied to Kohn-Sham (KS) functionals as well as orbital-density-dependent (ODD) functionals including explicit self-interaction correction. The implementation for KS functionals involves two nested loops: (1) An inner loop for finding a stationary point in a subspace spanned by the occupied and a few virtual orbitals corresponding to the excited state; (2) an outer loop for minimizing the energy in a tangential direction in the space of the orbitals. For ODD functionals, a third loop is used to find the unitary transformation that minimizes the energy functional among occupied orbitals only. Combined with the maximum overlap method, the algorithm converges in challenging cases where conventional self-consistent field algorithms tend to fail. The benchmark tests presented include two charge-transfer excitations in nitrobenzene and an excitation of CO to degenerate π* orbitals where the importance of complex orbitals is illustrated. The application of this method to several metal-to-ligand charge-transfer and metal-centered excited states of an FeII photosensitizer complex is described, and the results are compared to reported experimental estimates. This method is also used to study the effect of the Perdew-Zunger self-interaction correction on valence and Rydberg excited states of several molecules, both singlet and triplet states, and the performance compared to semilocal and hybrid functionals.

Mn Dimer Can Be Described Accurately with Density Functional Calculations When Self-Interaction Correction Is Applied.

Qualitatively incorrect results are obtained for the Mn dimer in density functional theory calculations using the generalized gradient approximation (GGA), and similar results are obtained from local density and meta-GGA functionals. The coupling is predicted to be ferromagnetic rather than antiferromagnetic, and the bond between the atoms is predicted to be an order of magnitude too strong and approximately an Ångstrøm too short. Explicit, self-interaction correction (SIC) applied to a commonly used GGA energy functional, however, provides close agreement with both experimental data and high-level, multireference wave function calculations. These results show that the failure is not due to a strong correlation but rather the single electron self-interaction that is necessarily introduced in estimates of the classical Coulomb and exchange-correlation energy when only the total electron density is used as the input. The corrected functional depends explicitly on the orbital densities and can, therefore, avoid the introduction of a self-Coulomb interaction. The error arises because of an overstabilization of bonding d-states in the minority spin channel resulting from an overestimate of the d-electron self-interaction in the semilocal exchange-correlation functionals. Since the computational effort in the SIC calculations scales with the system size in the same way as for regular semilocal functional calculations, this approach provides a way to calculate properties of Mn nanoclusters as well as biomolecules and extended solids, where Mn dimers and larger cluster are present, while multireference wave function calculations can only be applied to small systems.

Variational Density Functional Calculations of Excited States via Direct Optimization.

The development of variational density functional theory approaches to excited electronic states is impeded by limitations of the commonly used self-consistent field (SCF) procedure. A method based on a direct optimization approach as well as the maximum overlap method is presented, and the performance is compared with previously proposed SCF strategies. Excited-state solutions correspond to saddle points of the energy as a function of the electronic degrees of freedom. The approach presented here makes use of a preconditioner determined with the help of the maximum overlap method to guide the convergence on a target nth-order saddle point. This method is found to be more robust and converge faster than previously proposed SCF approaches for a set of 89 excited states of molecules. A limited-memory formulation of the symmetric rank-one method for updating the inverse Hessian is found to give the best performance. A conical intersection for the carbon monoxide molecule is calculated without resorting to fractional occupation numbers. Calculations on the excited states of the hydrogen atom and a doubly excited state of the dihydrogen molecule using a self-interaction corrected functional are presented. For these systems, the self-interaction correction is found to improve the accuracy of density functional calculations of excited states.

Multiple minimum-energy paths and scenarios of unwinding transitions in chiral nematic liquid crystals.

We apply the minimum-energy paths (MEPs) approach to study the helix unwinding transition in chiral nematic liquid crystals. A mechanism of the transition is determined by a MEP passing through a first order saddle point on the free energy surface. The energy difference between the saddle point and the initial state gives the energy barrier of the transition. Two starting approximations for the paths are used to find the MEPs representing different transition scenarios: (a) the director slippage approximation with in-plane helical structures and (b) the anchoring breaking approximation that involves the structures with profound out-of-plane director deviations. It is shown that, at sufficiently low voltages, the unwinding transition is solely governed by the director slippage mechanism with the planar saddle-point structures. When the applied voltage exceeds its critical value below the threshold of the Fréedericksz transition, the additional scenario through the anchoring breaking transitions is found to come into play. For these transitions, the saddle-point structure is characterized by out-of-plane deformations localized near the bounding surface. The energy barriers for different paths of transitions are computed as a function of the voltage and the anchoring energy strengths.