Perspective: Fifty years of density-functional theory in chemical physics

Becke, Axel D.

doi:10.1063/1.4869598

Cited by 1,288 publications

(1,030 citation statements)

References 231 publications

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“…In order to gain more insight into the energetics at stake in the crystals of 1 and 2, a DFT study was carried out on simplified models 8-8-9 and 8-8-10 of these crystals ( Figure 5) [68][69][70][71]. Two DFT methods were applied to study these systems, namely the widely used B3LYP functional as well as the M06-2X method known to be more suitable to treat weak interactions and peptides [74,75].…”

Section: Computational Studiesmentioning

confidence: 99%

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Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

et al. 2016

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Isomorphous crystals of two diacetylene derivatives with carbamate functionality (BocNH-CH 2 -diyne-X, where X = H or Br) have been obtained. The main feature of these structures is the original 2D arrangement (as supramolecular sheets or walls) in which the H bond and halogen bond have a prominent effect on the whole architecture. The two diacetylene compounds harbor neighboring carbamate (Boc protected amine) and conjugated alkyne functionalities. They differ only by the nature of the atom located at the penultimate position of the diyne moiety, either a hydrogen atom or a bromine atom. Both of them adopt very similar 2D wall organizations with antiparallel carbamates (as in antiparallel beta pleated sheets). Additional weak interactions inside the same walls between molecular bricks are H bond interactions (diyne-H¨¨¨O=C) or halogen bond interactions (diyne-Br¨¨¨O=C), respectively. Based on crystallographic atom coordinates, DFT (B3LYP/6-31++G(d,p)) and DFT (M06-2X/6-31++G(d,p)) calculations were performed on these isostructural crystals to gain insight into the intermolecular interactions.

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Section: Computational Studiesmentioning

confidence: 99%

Section: Computational Studiesmentioning

confidence: 99%

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

et al. 2016

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“…Approximate density functional theory (DFT) remains the method of choice for computational discovery [4][5][6][7][8][9][10][11] , owing to its favorable balance of accuracy and efficiency. 12 Nevertheless, delocalization errors [13][14] and other biases in semi-local exchange approximations [15][16] (e.g., the generalized gradient approximation or GGA) produce systematic biases toward low-spin states [17][18] that prevent prediction of either qualitative (i.e., ground state identity) or quantitative (i.e., energetic splitting between states) spin-state properties. The bias toward low-spin states may be understood [19][20] by recalling the greater delocalization afforded through greater population of bonding orbitals in low-spin states than in high-spin states.…”

Section: Introductionmentioning

confidence: 99%

Ligand-Field-Dependent Behavior of Meta-GGA Exchange in Transition-Metal Complex Spin-State Ordering

2017

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Prediction of spin-state ordering in transition metal complexes is essential for understanding catalytic activity and designing functional materials. Semi-local approximations in density functional theory, such as the generalized-gradient approximation (GGA), suffer from several errors notably including delocalization error that give rise to systematic bias for more covalently bound low-spin electronic states. Incorporation of exact exchange is known to counteract this bias, instead favoring high-spin states, in a manner that has recently been identified to be ligand-field dependent. In this work, we introduce a tuning strategy to identify the effect of incorporating the Laplacian of the density (i.e., a meta-GGA) in exchange on spinstate ordering. We employ a diverse test set of M(II) and M(III) first-row transition metal ions from Ti to Cu as well as octahedral complexes of these ions with ligands of increasing field strength (i.e., H 2 O, NH 3 , and CO). We show that the sensitivity of spin-state ordering to meta-GGA exchange is highly ligand-field dependent, stabilizing high-spin states in strong-field (i.e., CO) cases and stabilizing low-spin states in weak-field (i.e., H 2 O, NH 3 , and isolated ions) cases. This diverging behavior leads to generally improved treatment of isolated ions and strong field complexes over a standard GGA but worsened treatment for the hexa-aqua or hexa-ammine complexes. These observations highlight the sensitivity of functional performance to subtle changes in chemical bonding.2

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“…In the 50 years since its conception, the range of molecular and solid-state properties to which is may be applied has grown enormously (see Refs. 3,4 for some recent perspectives). In all of these applications, the choice of approximate exchange-correlation functional is a governing factor in the accuracy that may be obtained from the simulations.…”

Section: Introductionmentioning

confidence: 99%

Alternative Representations of the Correlation Energy in Density‐Functional Theory: A Kinetic‐Energy Based Adiabatic Connection

Teale

Helgaker

Savin

2015

J Chinese Chemical Soc

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The adiabatic-connection framework has been widely used to explore the properties of the correlation energy in density-functional theory. The integrand in this formula may be expressed in terms of the electron-electron interactions directly, involving intrinsically two-particle expectation values. Alternatively, it may be expressed in terms of the kinetic energy, involving only one-particle quantities. In this work, we explore this alternative representation for the correlation energy and highlight some of its potential for the construction of new density functional approximations. The kineticenergy based integrand is effective in concentrating static correlation effects to the low interaction strength regime and approaches zero asymptotically, offering interesting new possibilities for modelling the correlation energy in density-functional theory.2

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Perspective: Fifty years of density-functional theory in chemical physics

Cited by 1,288 publications

References 231 publications

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

Ligand-Field-Dependent Behavior of Meta-GGA Exchange in Transition-Metal Complex Spin-State Ordering

Alternative Representations of the Correlation Energy in Density‐Functional Theory: A Kinetic‐Energy Based Adiabatic Connection

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