Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Mussard, Bastien; Reinhardt, Peter; Ángyán, János G.; Toulouse, Julien

doi:10.1063/1.4918710

Cited by 39 publications

(42 citation statements)

References 63 publications

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“…Most of these approximations account for the exchange interaction in RPA correlation and go beyond the SOSEX approximation. One of them is the rPT2 described above, but other approaches like RPAX2 42,43 and the recently developed RPAx-SO2 44 deliver also improvement beyond RPA. The AXK (approximate exchange kernel) approach is based on renormalization of the many-body perturbation theory (in a similar manner as rPT2) and provides a leading correction to RPA.…”

Section: Methodsmentioning

confidence: 99%

Insight into organic reactions from the direct random phase approximation and its corrections

Ruzsinszky

Zhang

Scheffler

2015

The Journal of Chemical Physics

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The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

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Section: Methodsmentioning

confidence: 99%

Insight into organic reactions from the direct random phase approximation and its corrections

Ruzsinszky

Zhang

Scheffler

2015

The Journal of Chemical Physics

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“…With srLDA as the underlying functional and no additional scaling of long-range correlation, the method performed similar to dRPA-srLDA on the aforementioned test sets, and gave slightly better result compared to the latter for activation and reaction enthalpies of 1,3-dipolar cycloadditions. 97 A study of Mussard et al 98,99 compared the accuracy of MP2-srDFT and RPA-srDFT for atomization energies from the AE49 dataset 100 and forward/reverse reaction barrier heights from the DBH24/08 dataset. 101 The RPAx-SO2-srDFT method with exchange, based on the Szabo and Ostlund's formulation, 102 combined with srPBE 21 was identified as one of the best-performing RPA schemes (the RPA correlation was not scaled).…”

Section: Thermochemistry and Kineticsmentioning

confidence: 99%

Range‐separated multiconfigurational density functional theory methods

Pernal

Hapka

2021

WIREs Comput Mol Sci

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Range-separated multiconfigurational density functional theory (RS MC-DFT) rigorously combines density functional (DFT) and wavefunction (WFT) theories. This is achieved by partitioning of the electron interaction operator into long-and short-range components and modeling them with WFT and DFT, respectively. In contrast to other methods, mixing wavefunctions with density functionals, RS MC-DFT is free from electron correlation double counting. The general formulation of RS MC-DFT allows for merging any ab initio approximation with density functionals. Implementations of RS MC-DFT aim at increasing both versatility and accuracy of the underlying methods, while reducing the computational cost of the ab initio problem. Variants of the RS MC-DFT approach can be divided into single-determinant-based range-separated methods and range-separated multideterminantal WFT methods. In these approaches the electron correlation energy is described both by a pertinent short-range density functional and by the wavefunction theory. We review the short-range functionals and correlated wavefunction theories employed in the framework of RS MC-DFT. We discuss applications of the RS MC-DFT methods to ground-state properties of molecules and to noncovalent interactions. Time-dependent linear-response theory and direct approaches to excited states are also presented. For each area of applications, we assess advantages of RS MC-DFT over conventional DFT and ab initio methods.

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“…It was found that srDFT-lrRPA methods are particularly suitable to describe intermolecular interaction energies with good accuracies at a moderate computational cost in comparison with corresponding (full-range) wave function methods [54,75,76]. Moreover, several lrRPA methods have been tested for describing atomisation energies as well as a range of other thermokinetic properties and it has been observed that on average the range-separated RPA methods perform better than their full-range RPA counterparts [79,80]. Paier et al [79] could demonstrate that range-separated RPA approaches are able to resolve the strong delocalisation errors of the full-range RPA methods that lead to qualitatively wrong dissociation curves of some charged diatomic molecules.…”

Section: Introductionmentioning

confidence: 99%

Assessment of a range-separated orbital-optimised random-phase approximation electron correlation method

Heßelmann

Ángyán

2018

Theor Chem Acc

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A range-separated short-range DFT (density functional theory) long-range RPA (random-phase approximation) electron correlation method has been derived that is fully optimised with respect to variations in the orbitals and orbital eigenvalues. The method both exhibits a reduced dependence on the basis set size compared to the full-range RPA correlation method and can be implemented with a computational algorithm which scales only with the fourth power of the molecular size, thus is feasible also for describing large electronic systems. The performance of the functional has been tested for describing the reaction energies of a set of 16 chemical reactions as well as for describing first-order electric properties. In these studies, the influence of the range-separation parameter on the results has been analysed. Utilising accurate coupled-cluster results as a reference, it will be shown that at values of = 1.0 − 2.0 higher accuracies relative to the full-range DFT functional (corresponding to = 0 ) on the one hand and the full-range RPA functional (corresponding to = ∞ ) on the other hand can be achieved.

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Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

Cited by 39 publications

References 63 publications

Insight into organic reactions from the direct random phase approximation and its corrections

Insight into organic reactions from the direct random phase approximation and its corrections

Range‐separated multiconfigurational density functional theory methods

Assessment of a range-separated orbital-optimised random-phase approximation electron correlation method

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