Ensemble Generalization of the Perdew-Zunger Self-Interaction Correction: A Way Out of Multiple Minima and Symmetry Breaking.

The Perdew-Zunger (PZ) self-interaction correction (SIC) is an established tool to correct unphysical behavior in density functional approximations. Yet, the PZ-SIC is well-known to sometimes break molecular symmetries. An example of this is the benzene molecule, for which the PZ-SIC predicts a symmetry-broken electron density and molecular geometry, since the method does not describe the two possible Kekulé structures on an even footing, leading to local minima [Lehtola et al.

Ultrafast Heating-Induced Suppression of -Band Dominance in the Electronic Excitation Spectrum of Cuprum.

The combination of isochoric heating of solids by free-electron lasers (FELs) and in situ diagnostics by X-ray Thomson scattering (XRTS) allows for measurements of material properties at warm dense matter (WDM) conditions relevant for astrophysics, inertial confinement fusion, and materials science. In the case of metals, the FEL beam pumps energy directly into electrons with the lattice structure of ions being nearly unaffected. This leads to a unique transient state that gives rise to a set of interesting physical effects, which can serve as a reliable testing platform for WDM theories.

Ab initio path integral Monte Carlo simulations of warm dense two-component systems without fixed nodes: Structural properties.

We present extensive new ab initio path integral Monte Carlo (PIMC) results for a variety of structural properties of warm dense hydrogen and beryllium. To deal with the fermion sign problem-an exponential computational bottleneck due to the antisymmetry of the electronic thermal density matrix-we employ the recently proposed [Y. Xiong and H.

Path Integral Monte Carlo Simulations of the Uniform Electron Gas on Large Length Scales.

The accurate description of non-ideal quantum many-body systems is of prime importance for a host of applications within physics, quantum chemistry, materials science, and related disciplines. At finite temperatures, the gold standard is given by path integral Monte Carlo (PIMC) simulations, which do not require any empirical input but exhibit an exponential increase in the required computation time for Fermionic systems with an increase in system size . Very recently, computing Fermionic properties without this bottleneck based on PIMC simulations of fictitious identical particles has been suggested.

Bound-State Breaking and the Importance of Thermal Exchange-Correlation Effects in Warm Dense Hydrogen.

Hydrogen at extreme temperatures and pressures is of key relevance for cutting-edge technological applications, with inertial confinement fusion research being a prime example. In addition, it is ubiquitous throughout our universe and naturally occurs in a variety of astrophysical objects. In the present work, we present exact ab initio path integral Monte Carlo (PIMC) results for the electronic density of warm dense hydrogen along a line of constant degeneracy across a broad range of densities.

Bond formation insights into the Diels-Alder reaction: A bond perception and self-interaction perspective.

The behavior of electrons during bond formation and breaking cannot commonly be accessed from experiments. Thus, bond perception is often based on chemical intuition or rule-based algorithms. Utilizing computational chemistry methods, we present intrinsic bond descriptors for the Diels-Alder reaction, allowing for an automatic bond perception.

How good are recent density functionals for ground and excited states of one-electron systems?

Sun et al. [J. Chem.

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.

porE: A code for deterministic and systematic analyses of porosities.

Accurate numerical calculations of porosities and related properties are of importance when analyzing metal-organic frameworks (MOFs). We present porE, an open-source, general-purpose implementation to compute such properties and discuss all results regarding their sensitivity to numerical parameters. Our code combines the numerical efficiency of Fortran with the user-friendliness of Python.

PyFLOSIC: Python-based Fermi-Löwdin orbital self-interaction correction.

We present pyflosic, an open-source, general-purpose python implementation of the Fermi-Löwdin orbital self-interaction correction (FLO-SIC), which is based on the python simulation of chemistry framework (pyscf) electronic structure and quantum chemistry code. Thanks to pyscf, pyflosic can be used with any kind of Gaussian-type basis set, various kinds of radial and angular quadrature grids, and all exchange-correlation functionals within the local density approximation, generalized-gradient approximation (GGA), and meta-GGA provided in the libxc and xcfun libraries. A central aspect of FLO-SIC is the Fermi-orbital descriptors, which are used to estimate the self-interaction correction.

Interpretation and Automatic Generation of Fermi-Orbital Descriptors.

We present an interpretation of Fermi-orbital descriptors (FODs) and argue that these descriptors carry chemical bonding information. We show that a bond order derived from these FODs agrees well with reference values, and highlight that optimized FOD positions used within the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method correspond to expectations from Linnett's double-quartet theory, which is an extension of Lewis theory. This observation is independent of the underlying exchange-correlation functional, which is shown using the local spin density approximation, the Perdew-Burke-Ernzerhof generalized gradient approximation (GGA), and the strongly constrained and appropriately normed meta-GGA.

Stretched or noded orbital densities and self-interaction correction in density functional theory.

Semilocal approximations to the density functional for the exchange-correlation energy of a many-electron system necessarily fail for lobed one-electron densities, including not only the familiar stretched densities but also the less familiar but closely related noded ones. The Perdew-Zunger (PZ) self-interaction correction (SIC) to a semilocal approximation makes that approximation exact for all one-electron ground- or excited-state densities and accurate for stretched bonds. When the minimization of the PZ total energy is made over real localized orbitals, the orbital densities can be noded, leading to energy errors in many-electron systems.

Analytic atomic gradients in the fermi-löwdin orbital self-interaction correction.

We derived, implemented, and thoroughly tested the complete analytic expression for atomic forces, consisting of the Hellmann-Feynman term and the Pulay correction, for the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method. Analytic forces are shown to be numerically accurate through an extensive comparison to forces obtained from finite differences. Using the analytic forces, equilibrium structures for a small set of molecules were obtained.

Fermi-Löwdin orbital self-interaction corrected density functional theory: Ionization potentials and enthalpies of formation.

The Fermi-Löwdin orbital self-interaction correction (FLO-SIC) methodology is applied to atoms and molecules from the standard G2-1 test set. For the first time FLO-SIC results for the GGA-type PBE functional are presented. In addition, examples where FLO-SIC like any proper SIC provides qualitative improvements compared to standard DFT functionals are discussed in detail: the dissociation limit for , the step-wise linearity behavior for fractional occupation, as well as the significant reduction of the error of static polarizabilities.

Theoretical and experimental investigations of Xe NMR chemical shift isotherms in metal-organic frameworks.

The pressure dependence of the 129Xe chemical shift in the metal-organic frameworks (MOFs) UiO-66 and UiO-67 (UiO - University of Oslo) has been investigated using both theory and experiment. The resulting chemical shift isotherms were analyzed with a theoretical approach based on model systems (as proposed by K. Trepte, J.

Symmetry Breaking within Fermi-Löwdin Orbital Self-Interaction Corrected Density Functional Theory.

Fermi-Löwdin orbital self-interaction corrected density functional theory (FLO-SIC DFT) is applied to CH, NO, O, and CH. In general our results indicate that FLO-SIC does favor symmetric setups for molecules with nontrivial chemical bonding. Further we discuss two types of possible symmetry breaking.

The origin of the measured chemical shift of Xe in UiO-66 and UiO-67 revealed by DFT investigations.

The NMR chemical shift of the xenon isotope Xe inside the metal-organic frameworks (MOFs) UiO-66 and UiO-67 (UiO - University of Oslo) has been investigated both with density functional theory (DFT) and in situ high-pressure Xe NMR measurements. The experiments reveal a decrease of the total chemical shift comparing the larger isoreticular MOF (UiO-67) with the smaller one (UiO-66), even though one may expect an increase due to the higher amount of adsorbed Xe atoms. We are able to calculate contributions to the chemical shift individually.

Ni formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties.

The synthesis of four Ni formate complexes of the type [Ni(NN)][OCH] (2, adduct with 3/4 EtOH, NN = en, e[combining low line]thylen[combining low line]ediamine, n = 3; 4, NN = dien, N,N',N''-d[combining low line]i[combining low line]e[combining low line]thylen[combining low line]etriamine, n = 2), [Ni(OCH)(HO)(tmeda)] (3, tmeda = N,N,N',N'-t[combining low line]etram[combining low line]ethyle[combining low line]thylened[combining low line]ia[combining low line]mine) and [{Ni(OCH)(pmdta)}·HO] (5, pmdta = N,N',N',N'',N''-p[combining low line]entam[combining low line]ethyld[combining low line]iethylenet[combining low line]ria[combining low line]mine) by a reaction of [{Ni(OCH)}·2HO] (1) with the respective N-donor bases is reported. The structures of 2-5 in the solid state were determined by single X-ray structure analysis, revealing a discrete dinuclear structure of 3 and the formation of polymeric networks in the case of 2, 4 and 5 due to intermolecular hydrogen bonding. SQUID and ESR measurements of 3 evidenced a weak antiferromagnetic coupling between the Ni ions and an easy plane magnetic anisotropy.

Screening for high-spin metal organic frameworks (MOFs): density functional theory study on DUT-8(M1,M2) (with Mi = V,…,Cu).

We present a first principles study of low-spin (LS)/high-spin (HS) screening for 3d metal centers in the metal organic framework (MOF) DUT-8(Ni). Various density functional theory (DFT) codes have been used to evaluate numerical and DFT related errors. We compare highly accurate all-electron implementations with the widely used plane wave approach.

Correction: Electronic and magnetic properties of DUT-8(Ni).

Correction for 'Electronic and magnetic properties of DUT-8(Ni)' by Kai Trepte et al., Phys. Chem.

Electronic and magnetic properties of DUT-8(Ni).

First principles calculations using density functional theory (DFT) have been performed to investigate the electronic and magnetic properties of DUT-8(Ni) (DUT - Dresden University of Technology). This flexible metal-organic framework (MOF) exists in two crystalline forms: DUT-8(Ni)open and DUT-8(Ni)closed. To identify the energetically favoured magnetic ordering, the density of states (DOS) and the energy difference between a low-spin (LS) and a high-spin (HS) coupling ΔELS-HS for those crystalline structures have been computed.