A coupled cluster treatment of intramonomer electron correlation within symmetry-adapted perturbation theory: benchmark calculations and a comparison with a density-functional theory description

Korona, Tatiana

doi:10.1080/00268976.2012.746478

Cited by 64 publications

(102 citation statements)

References 77 publications

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“…Similar overbinding in DFT-SAPT was reported for dispersion dominated systems containing phosphorus, (P 2 ) 2 and (PCCP) 2 , in Ref. 80.…”

Section: A24 and Di6-04 Test Resultssupporting

confidence: 84%

“…We observe that optimally tuned LRC functionals stay in close agreement and outperform asymptotically corrected PBE0AC, considered as the functional of choice for the DFT-SAPT method. 5,80 In the case of the dipole-bound systems in the DI6-04 data set, the situation is different, as the increased fraction of the HF exchange correlates with a considerable overbinding. There is a clear deterioration from PBEAC to PBE0AC and analogously from LRC-ωPBE to LRC-ωPBEh, with PBE0AC and LRC-ωPBE performing almost identically.…”

Section: A24 and Di6-04 Test Resultsmentioning

confidence: 99%

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Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Hapka

Rajchel

Modrzejewski

et al. 2014

The Journal of Chemical Physics

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The aim of this study is to present a performance test of optimally tuned long-range corrected (LRC) functionals applied to the symmetry-adapted perturbation theory (SAPT). In the present variant, the second-order energy components are evaluated at the coupled level of theory. We demonstrate that the generalized Kohn-Sham (GKS) description of monomers with optimally tuned LRC functionals may be essential for the quality of SAPT interaction energy components. This is connected to the minimization of a many-electron self-interaction error and exemplified by two model systems: polyacetylenes of increasing length and stretching of He 3 (+). Next we provide a comparison of SAPT approaches based on Kohn-Sham and GKS description of the monomers. We show that LRC leads to results better or comparable with the hitherto prevailing asymptotically corrected functionals. Finally, we discuss the advantages and possible limitations of SAPT based on LRC functionals.

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“…Similar overbinding in DFT-SAPT was reported for dispersion dominated systems containing phosphorus, (P 2 ) 2 and (PCCP) 2 , in Ref. 80.…”

Section: A24 and Di6-04 Test Resultssupporting

confidence: 84%

Section: A24 and Di6-04 Test Resultsmentioning

confidence: 99%

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Hapka

Rajchel

Modrzejewski

et al. 2014

The Journal of Chemical Physics

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“…We note that at this level of SAPT(DFT), the water dimer is bound already at rst order (albeit insignicantly!). This result can be compared with the previous ndings of Korona 44 (see Table 4 there), where a number of dierent density functionals were employed to describe the intramolecular electron correlation. There, it was found that for some density functionals (e.g., M05-2X and M06) the water dimer is bound at rst order, whereas for some others (e.g., LDA and PBE) it is not.…”

Section: Resultsmentioning

confidence: 74%

“…52 ) and conrmed in ref. 44 . We should note that the use of the so-called S 2 approximation (or single- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 exchange of electrons) for the evaluation of both the second-order exchange-induction, E (2) exch−ind , and exchange-dispersion, E (2) exch−disp , terms can result in the underestimation 87 and overestimation, 88 respectively, of these terms especially at shorter intermolecular separations.…”

Section: Resultsmentioning

confidence: 99%

Challenging Dogmas: Hydrogen Bond Revisited

Tafipolsky

2016

J. Phys. Chem. A

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Hydrogen bond directionality in the water dimer is explained on the basis of symmetry-adapted intermolecular perturbation theory which directly separates the intermolecular interaction energy into four physically interpretable components: electrostatics, exchange-repulsion, dispersion, and induction. Analysis of these four main contributions to the binding energy allows a deeper understanding of the dominant factors ruling the mutual arrangement of the two monomers. A preference for the linear configuration is shown to be due to a subtle interplay of all four energy components. While the first-order terms, electrostatic and exchange-repulsion, almost perfectly cancel each other near the equilibrium geometry of the dimer, the importance of the second- and higher-order terms, induction and dispersion, becomes evident.

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“…If wavefunction theory is used for the SAPT expansion, many choices of truncation are available, including complete neglect of the intramolecular correlation potentials [SAPT0], 24 many-body treatment of the intramolecular correlation potentials and/or higher-order terms [SAPT2, SAPT2+, SAPT2+(3), SAPT2+3], 24,[28][29][30] infinite-order treatment of certain terms [SAPT2+(CCD), SAPT2+(3)(CCD), SAPT2+3(CCD)], [31][32][33] or expansion of the monomer susceptibility functions [SAPT(CCSD), etc.]. [34][35][36][37][38] Additionally, much progress has been made recently in adapting Kohn-Sham density functional theory (DFT) to the SAPT environment, resulting in the closely related SAPT(DFT) and DFT-SAPT methods with excellent accuracy to cost ratios. [39][40][41][42][43] Most variants of SAPT are designed for dimer interactions, though trimer [44][45][46] and even hybrid many-monomer 47,48 flavors also exist.…”

Section: Introductionmentioning

confidence: 99%

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

Parrish

Sherrill

2014

The Journal of Chemical Physics

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We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work through the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-π interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.

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A coupled cluster treatment of intramonomer electron correlation within symmetry-adapted perturbation theory: benchmark calculations and a comparison with a density-functional theory description

Cited by 64 publications

References 77 publications

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Challenging Dogmas: Hydrogen Bond Revisited

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

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