A Parameter-Free Density Functional That Works for Noncovalent Interactions

Eshuis, Hendrik; Furche, Filipp

doi:10.1021/jz200238f

Cited by 143 publications

(166 citation statements)

References 78 publications

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“…72. As recent results already showed for the dRPA case, 32,35,36 RPAmethods yield quite accurate interaction energies for noncovalent and weakly bonded dimers. This is confirmed here.…”

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodssupporting

confidence: 62%

“…Besides this, the influence of the input orbitals in dRPA calculations can be seen by comparing the RI-dRPA values of this work based on EXX orbitals and eigenvalues with the TPSS-RI-dRPA results of Ref. 35 based on orbitals and eigenvalues obtained with the TPSS exchange-correlation functional.…”

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 92%

“…The finding that RI-dRPA reaction energies are quite accurate again is in line with earlier findings. 33,35 Figure 10 shows potential energy surfaces for the twisting of the CH 2 groups of ethene against each other around the carbon-carbon bond. At a twisting angle of 90…”

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 99%

“…23 (denoted here as TPSS-RI-dRPA), which was also tested on the S22 database using orbitals generated with the TPSS functional 41 as input for the RPA calculation. 35 In Table II RI-EXXRPA+, RI-EXXRPA, RI-dRPA, MP2, F12-CCSD, and TPSS-RI-dRPA interaction energies are compared to the CCSD(T) reference from Ref. 72.…”

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 99%

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Resolution of identity approach for the Kohn-Sham correlation energy within the exact-exchange random-phase approximation

Bleiziffer

Heßelmann

Görling

2012

The Journal of Chemical Physics

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Two related methods to calculate the Kohn-Sham correlation energy within the framework of the adiabatic-connection fluctuation-dissipation theorem are presented. The required coupling-strengthdependent density-density response functions are calculated within exact-exchange time-dependent density-functional theory, i.e., within time-dependent density-functional response theory using the full frequency-dependent exchange kernel in addition to the Coulomb kernel. The resulting resolution-of-identity exact-exchange random-phase approximation (RI-EXXRPA) methods in contrast to previous EXXRPA methods employ an auxiliary basis set (RI basis set) to improve the computational efficiency, in particular, to reduce the formal scaling of the computational effort with respect to the system size N from N 6 to N 5 . Moreover, the presented RI-EXXRPA methods, in contrast to previous ones, do not treat products of occupied times unoccupied orbitals as if they were linearly independent. Finally, terms neglected in previous EXXRPA methods can be included, which leads to a method designated RI-EXXRPA+, while the method without these extra terms is simply referred to as RI-EXXRPA. Both EXXRPA methods are shown to yield total energies, reaction energies of small molecules, and binding energies of noncovalently bonded dimers of a quality that is similar and in some cases even better than that obtained with quantum chemistry methods such as Møller-Plesset perturbation theory of second order (MP2) or with the coupled cluster singles doubles method. In contrast to MP2 and to conventional density-functional methods, the presented RI-EXXRPA methods are able to treat static correlation.

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“…72. As recent results already showed for the dRPA case, 32,35,36 RPAmethods yield quite accurate interaction energies for noncovalent and weakly bonded dimers. This is confirmed here.…”

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodssupporting

confidence: 62%

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 92%

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 99%

Section: B Comparison Of the Accuracy Of Ri-exxrpa And Other Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Resolution of identity approach for the Kohn-Sham correlation energy within the exact-exchange random-phase approximation

Bleiziffer

Heßelmann

Görling

2012

The Journal of Chemical Physics

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“…It is interesting to note that the PBE0-∞D interaction energies in Table II are in some cases more accurate with respect to the CCSD(T) reference than those determined from exactexchange with RPA correlation computed based on DFT orbitals (EX+cRPA). 76 On one hand, this finding can be explained by more accurate Tkatchenko-Scheffler 68 molecular polarizabilities utilized as input in the DFT-∞D approach. On the other hand, there is one empirical parameter employed when coupling the DFT energy with the long-range dispersion energy in the DFT-∞D approach, while the EX+cRPA method is parameter-free.…”

mentioning

confidence: 99%

Interatomic methods for the dispersion energy derived from the adiabatic connection fluctuation-dissipation theorem

Tkatchenko¹,

Ambrosetti²,

DiStasio³

2013

The Journal of Chemical Physics

156

220

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Derivation of the dispersion energy as an explicit density-and exchange-hole functional J. Chem. Phys. 130, 084104 (2009) Interatomic pairwise methods are currently among the most popular and accurate ways to include dispersion energy in density functional theory calculations. However, when applied to more than two atoms, these methods are still frequently perceived to be based on ad hoc assumptions, rather than a rigorous derivation from quantum mechanics. Starting from the adiabatic connection fluctuationdissipation (ACFD) theorem, an exact expression for the electronic exchange-correlation energy, we demonstrate that the pairwise interatomic dispersion energy for an arbitrary collection of isotropic polarizable dipoles emerges from the second-order expansion of the ACFD formula upon invoking the random-phase approximation (RPA) or the full-potential approximation. Moreover, for a system of quantum harmonic oscillators coupled through a dipole-dipole potential, we prove the equivalence between the full interaction energy obtained from the Hamiltonian diagonalization and the ACFD-RPA correlation energy. This property makes the Hamiltonian diagonalization an efficient method for the calculation of the many-body dispersion energy. In addition, we show that the switching function used to damp the dispersion interaction at short distances arises from a short-range screened Coulomb potential, whose role is to account for the spatial spread of the individual atomic dipole moments. By using the ACFD formula, we gain a deeper understanding of the approximations made in the interatomic pairwise approaches, providing a powerful formalism for further development of accurate and efficient methods for the calculation of the dispersion energy.

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Quantum Chemical Calculation of Tautomeric Equilibria

Fabian

2013

Tautomerism

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IntroductionTautomerism can be considered as a special case of isomerism where the movement of an atom or group of atoms between two sites occurs rapidly enough to establish chemical equilibrium at room temperature. Hence, both thermodynamic as well as kinetic criteria have to be used to draw an approximate distinction line between tautomerism and conventional isomerism. Assuming a lower limit of K = 10 −8 for the experimental determination of equilibrium constants and a rate constant of k = 10 −5 s −1 distinguishing mobile systems from stable ones, at room temperature G • < 8 kcal mol −1 and G = < 25 kcal mol −1 characterize a tautomeric system [1]. Most interconversion between the individual species occurs by movement of a hydrogen atom (prototropism), as in simple keto-enol [2], lactam-lactim, and annular prototropism in heterocycles [3], or azo-hydrazo [4] tautomerism. Transformation between tautomeric structures by movement of atoms other than hydrogen involves formation of cyclic acetals/ketals, for example, furanose/pyranose forms of sugars, ring-chain tautomerism in oxo carboxylic acid derivatives [1], or azido-tetrazole and related equilibria [5]. Coping with tautomeric equilibria has become a hot topic in chemoinformatics as well as drug discovery. Obviously, reliable predictions of tautomeric equilibria by computational procedures would be of great help. This importance is also revealed by the fact that in the third round of the statistical assessment of the modeling of proteins and ligands (SAMPL) challenge (SAMPL2) the calculation of tautomer energies was included [6]. However, as stated by Martin [7], ''In summary, although quantum chemical calculations provide much insight into the relative energies of tautomers, there appears to be no consensus on the optimal method.'' Frequently, energy differences are quite small and hence require very accurate calculations which can be fiendishly difficult. Thus, the choice of an appropriate electronic structure procedure is very important. Furthermore, environmental influences (solvent) have a profound effect on the position of tautomeric equilibria. Consequently, a proper description of solvation is essential. Alternatively, some property that might be useful to distinguish between tautomers could be Tautomerism: Methods and Theories, First Edition. Edited by Liudmil Antonov.

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A Parameter-Free Density Functional That Works for Noncovalent Interactions

Abstract: b S Supporting Information M edium-and long-range noncovalent interactions play a vital role in many chemical systems and processes, such as

Cited by 143 publications

References 78 publications

Resolution of identity approach for the Kohn-Sham correlation energy within the exact-exchange random-phase approximation

Resolution of identity approach for the Kohn-Sham correlation energy within the exact-exchange random-phase approximation

Interatomic methods for the dispersion energy derived from the adiabatic connection fluctuation-dissipation theorem

Quantum Chemical Calculation of Tautomeric Equilibria

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