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Themed collection Developments in Density Functional Theory

32 articles
Editorial

Editorial for PCCP themed issue “Developments in Density Functional Theory”

This issue provides an overview of the state-of-the-art of DFT, ranging from mathematical and software developments, via topics in chemical bonding theory, to all kinds of molecular and material properties. Through this issue, we also celebrate the enormous contributions that Evert Jan Baerends has made to this field.

Graphical abstract: Editorial for PCCP themed issue “Developments in Density Functional Theory”
From the themed collection: Developments in Density Functional Theory
Perspective

How molecular is the chemisorptive bond?

Scaling rules differ for early and late transition metals. Their electronic structure and topological bond analysis are shown.

Graphical abstract: How molecular is the chemisorptive bond?
From the themed collection: Developments in Density Functional Theory
Paper

Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst

We present an ab initio molecular dynamics approach to characterize proton-coupled electron transfer catalytic steps and identify the preferred reaction mechanism.

Graphical abstract: Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst
From the themed collection: Developments in Density Functional Theory
Open Access Paper

First hyperpolarizability of para-aminoaniline induced by a variety of gold nano particles

Molecules exposed to an electromagnetic field due to the presence of nearby nanoparticles are known to be affected.

Graphical abstract: First hyperpolarizability of para-aminoaniline induced by a variety of gold nano particles
From the themed collection: Developments in Density Functional Theory
Paper

Revisiting an old concept: the coupled oscillator model for VCD. Part 2: implications of the generalised coupled oscillator mechanism for the VCD robustness concept

The generalised coupled oscillator (GCO) mechanism implies that the stability of the computed VCD sign should be assigned by monitoring the uncertainties in the relative orientation of the GCO fragments and in the nuclear displacement vectors, i.e. not the magnitude of the dissymmetry factor.

Graphical abstract: Revisiting an old concept: the coupled oscillator model for VCD. Part 2: implications of the generalised coupled oscillator mechanism for the VCD robustness concept
From the themed collection: Developments in Density Functional Theory
Paper

Revisiting an old concept: the coupled oscillator model for VCD. Part 1: the generalised coupled oscillator mechanism and its intrinsic connection to the strength of VCD signals

This work reports the development of a generalised coupled oscillator expression for VCD that is exact within the harmonic approximation and is applicable to all types of normal modes, regardless whether the considered molecule is symmetric or asymmetric.

Graphical abstract: Revisiting an old concept: the coupled oscillator model for VCD. Part 1: the generalised coupled oscillator mechanism and its intrinsic connection to the strength of VCD signals
From the themed collection: Developments in Density Functional Theory
Paper

An ab initio molecular dynamics study of D2 dissociation on CO-precovered Ru(0001)

In dynamics studies of hydrogen dissociation on CO pre-covered Ru(0001) the simulation cell size is important for describing energy exchange.

Graphical abstract: An ab initio molecular dynamics study of D2 dissociation on CO-precovered Ru(0001)
From the themed collection: Developments in Density Functional Theory
Open Access Paper

The role of alkali metal cations in the stabilization of guanine quadruplexes: why K+ is the best

The desolvation and size of monovalent alkali metal ions are of equal importance for the cation affinity of guanine quadruplexes.

Graphical abstract: The role of alkali metal cations in the stabilization of guanine quadruplexes: why K+ is the best
From the themed collection: Developments in Density Functional Theory
Paper

Constrained subsystem density functional theory

Constrained Subsystem Density Fucntional Theory (CSDFT) allows to compute diabatic states for charge transfer reactions using the machinery of the constrained DFT method, and at the same time is able to embed such diabatic states in a molecular environment via a subsystem DFT scheme.

Graphical abstract: Constrained subsystem density functional theory
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Magnetic properties with multiwavelets and DFT: the complete basis set limit achieved

Multiwavelets are emerging as an attractive alternative to traditional basis sets such as Gaussian-type orbitals and plane waves.

Graphical abstract: Magnetic properties with multiwavelets and DFT: the complete basis set limit achieved
From the themed collection: Developments in Density Functional Theory
Paper

Performance of polarisation functionals for linear and nonlinear optical properties of bulk zinc chalcogenides ZnX (X = S, Se, and Te)

We calculated the frequency dependent macroscopic dielectric function and second-harmonic generation of cubic ZnS, ZnSe and ZnTe within time-dependent density-polarisation functional theory.

Graphical abstract: Performance of polarisation functionals for linear and nonlinear optical properties of bulk zinc chalcogenides ZnX (X = S, Se, and Te)
From the themed collection: Developments in Density Functional Theory
Paper

A broken-symmetry density functional study of structures, energies, and protonation states along the catalytic O–O bond cleavage pathway in ba3 cytochrome c oxidase from Thermus thermophilus

The [Fea3, CuB] dinuclear center states along the O–O bond cleavage pathway in ba3 cytochrome c oxidase have been studied using broken-symmetry density functional calculations.

Graphical abstract: A broken-symmetry density functional study of structures, energies, and protonation states along the catalytic O–O bond cleavage pathway in ba3 cytochrome c oxidase from Thermus thermophilus
From the themed collection: Developments in Density Functional Theory
Paper

New approaches for the calibration of exchange-energy densities in local hybrid functionals

A new derivation of semi-local calibration functions is proposed, to ameliorate the gauge problem of exchange-energy densities in local hybrid functionals.

Graphical abstract: New approaches for the calibration of exchange-energy densities in local hybrid functionals
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Analytical gradients for excitation energies from frozen-density embedding

Analytical excitation-energy gradients from frozen-density embedding–time-dependent density functional theory are derived and implemented, which are important for photochemistry in complex systems.

Graphical abstract: Analytical gradients for excitation energies from frozen-density embedding
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Time-dependent Dyson orbital theory

Probabilities of single ionization channels or double and multiple simultaneous ionization can be determined from exact master equations for time-dependent Dyson orbitals.

Graphical abstract: Time-dependent Dyson orbital theory
From the themed collection: Developments in Density Functional Theory
Paper

Numerical density-to-potential inversions in time-dependent density functional theory

We present an unconditionally stable TDDFT inversion algorithm based on a constrained partial differential equation optimization framework and capable of recovering highly singular potentials.

Graphical abstract: Numerical density-to-potential inversions in time-dependent density functional theory
From the themed collection: Developments in Density Functional Theory
Paper

Effect of metallation, substituents and inter/intra-molecular polarization on electronic couplings for hole transport in stacked porphyrin dyads

Hole transport properties for stacked porphyrins are analyzed with density functional theory.

Graphical abstract: Effect of metallation, substituents and inter/intra-molecular polarization on electronic couplings for hole transport in stacked porphyrin dyads
From the themed collection: Developments in Density Functional Theory
Paper

Reduced density matrix embedding. General formalism and inter-domain correlation functional

An embedding method for a one-electron reduced density matrix (1-RDM) is proposed.

Graphical abstract: Reduced density matrix embedding. General formalism and inter-domain correlation functional
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Planar vs. three-dimensional X62−, X2Y42−, and X3Y32− (X, Y = B, Al, Ga) metal clusters: an analysis of their relative energies through the turn-upside-down approach

Despite the fact that B and Al belong to the same group 13 elements, the B62− cluster prefers the planar D2h geometry, whereas Al62− favours the Oh structure, which is caused by orbital interactions.

Graphical abstract: Planar vs. three-dimensional X62−, X2Y42−, and X3Y32− (X, Y = B, Al, Ga) metal clusters: an analysis of their relative energies through the turn-upside-down approach
From the themed collection: Developments in Density Functional Theory
Paper

Time-dependent density functional theory beyond Kohn–Sham Slater determinants

Different choices of initial Kohn Sham wavefunction shape the time-dependent exchange–correlation potential.

Graphical abstract: Time-dependent density functional theory beyond Kohn–Sham Slater determinants
From the themed collection: Developments in Density Functional Theory
Paper

Origin of the step structure of molecular exchange–correlation potentials

The step structure of exact exchange–correlation potentials is linked to the properties of the average local electron energy (ALEE).

Graphical abstract: Origin of the step structure of molecular exchange–correlation potentials
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Frozen-density embedding theory with average solvent charge densities from explicit atomistic simulations

Besides molecular electron densities obtained within the Born–Oppenheimer approximation (ρB(r)) to represent the environment, the ensemble averaged density (〈ρB〉(r)) is also admissible in frozen-density embedding theory (FDET) [Wesolowski, Phys. Rev. A, 2008, 77, 11444].

Graphical abstract: Frozen-density embedding theory with average solvent charge densities from explicit atomistic simulations
From the themed collection: Developments in Density Functional Theory
Open Access Paper

The S66x8 benchmark for noncovalent interactions revisited: explicitly correlated ab initio methods and density functional theory

The S66x8 dataset for noncovalent interactions of biochemical relevance has been re-examined by means of CCSD(F12*)(T), DFT, and SAPT methods.

Graphical abstract: The S66x8 benchmark for noncovalent interactions revisited: explicitly correlated ab initio methods and density functional theory
From the themed collection: Developments in Density Functional Theory
Paper

Using the GVB Ansatz to develop ensemble DFT method for describing multiple strongly correlated electron pairs

Ensemble density functional theory (DFT) furnishes a rigorous theoretical framework for describing the non-dynamic electron correlation arising from (near) degeneracy of several electronic configurations.

Graphical abstract: Using the GVB Ansatz to develop ensemble DFT method for describing multiple strongly correlated electron pairs
From the themed collection: Developments in Density Functional Theory
Open Access Paper

The adiabatic strictly-correlated-electrons functional: kernel and exact properties

We investigate a number of formal properties of the adiabatic strictly-correlated electrons (SCE) functional, relevant for time-dependent potentials and for kernels in linear response time-dependent density functional theory.

Graphical abstract: The adiabatic strictly-correlated-electrons functional: kernel and exact properties
From the themed collection: Developments in Density Functional Theory
Paper

External orthogonality in subsystem time-dependent density functional theory

We present a subsystem TDDFT method which maintains inter-subsystem orbital orthogonality.

Graphical abstract: External orthogonality in subsystem time-dependent density functional theory
From the themed collection: Developments in Density Functional Theory
Paper

Kohn–Sham calculations of NMR shifts for paramagnetic 3d metal complexes: protocols, delocalization error, and the curious amide proton shifts of a high-spin iron(II) macrocycle complex

Ligand chemical shifts (pNMR shifts) are analyzed using DFT. A large difference in the amide proton shifts of a high-spin Fe(II) complex arises from O → Fe dative bonding which only transfers β spin density to the metal.

Graphical abstract: Kohn–Sham calculations of NMR shifts for paramagnetic 3d metal complexes: protocols, delocalization error, and the curious amide proton shifts of a high-spin iron(ii) macrocycle complex
From the themed collection: Developments in Density Functional Theory
Open Access Paper

No need for external orthogonality in subsystem density-functional theory

Contrary to previous claims, there is no formal need for enforcing external orthogonality in subsystem density-functional theory.

Graphical abstract: No need for external orthogonality in subsystem density-functional theory
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Avoiding the 4-index transformation in one-body reduced density matrix functional calculations for separable functionals

One of the major computational bottlenecks in one-body reduced density matrix functional is the evaluation of the approximate functionals due to a 4-index transformation. For separable functionals, the 4-index transformation can be avoided which leads to a significant better scaling.

Graphical abstract: Avoiding the 4-index transformation in one-body reduced density matrix functional calculations for separable functionals
From the themed collection: Developments in Density Functional Theory
Paper

4-Component relativistic calculations of L3 ionization and excitations for the isoelectronic species UO22+, OUN+ and UN2

4-Component relativistic calculations explore uranium 2p3/2 ionization and excitation in the isoelectronic series UO22+, OUN+ and UN2.

Graphical abstract: 4-Component relativistic calculations of L3 ionization and excitations for the isoelectronic species UO22+, OUN+ and UN2
From the themed collection: Developments in Density Functional Theory
Open Access Paper

Extension of the interacting quantum atoms (IQA) approach to B3LYP level density functional theory (DFT)

The recovery of the total molecular energy from the IQA energy components for a B3LYP wave function is now possible.

Graphical abstract: Extension of the interacting quantum atoms (IQA) approach to B3LYP level density functional theory (DFT)
From the themed collection: Developments in Density Functional Theory
Paper

A computationally efficient double hybrid density functional based on the random phase approximation

A new double hybrid density functional (PWRB95) based on GGA orbitals and RPA is presented and its performance is investigated compared to standard DFT and wavefunction methods.

Graphical abstract: A computationally efficient double hybrid density functional based on the random phase approximation
From the themed collection: Developments in Density Functional Theory
32 articles

About this collection

This themed issue highlights state-of-the-art density functional theory (DFT), ranging from mathematical development of the formalism, via software development and development of bonding and reactivity models through applications in physical, (in)organic, and biological/supramolecular chemistry. This issue coincides with the 70th birthday of Prof. Evert Jan Baerends, who has made a significant contribution to the field, and is guest edited by Robert van Leeuwen, Johannes Neugebauer, Lucas Visscher and F. Matthias Bickelhaupt.

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