Single-determinant-based symmetry-adapted perturbation theory without single-exchange approximation

Schäffer, Rainer; Jansen, Georg

doi:10.1080/00268976.2013.827253

Cited by 43 publications

(72 citation statements)

References 68 publications

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“…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. As a consequence, the second-order induction (dispersion) contribution is probably overestimated (underestimated) in our present study.…”

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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Section: Resultsmentioning

confidence: 99%

Challenging Dogmas: Hydrogen Bond Revisited

Tafipolsky

2016

J. Phys. Chem. A

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“…The net result is that the sSAPT0 interaction energy is always more positive than the SAPT0 one, empirically correcting some of the overbinding of the latter at short range. The recent derivation and implementation of the complete, nonapproximated

E_{exch ‐ ind, resp}^{(20)}

and

E_{exch ‐ disp}^{(20)}

corrections makes it possible to compute the entire SAPT0 interaction energy, Equation , without the single exchange approximation and to assess the adequacy of the scaling factors of Equation for different choices of the parameter α ; I will discuss these developments in more detail in Section 4.2.…”

Section: The Sapt Formalismmentioning

confidence: 99%

Recent developments in symmetry‐adapted perturbation theory

Patkowski

2019

WIREs Comput Mol Sci

147

144

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Symmetry-adapted perturbation theory (SAPT) is a well-established method to compute accurate intermolecular interaction energies in terms of physical effects such as electrostatics, induction (polarization), dispersion, and exchange. With many theory levels and variants, and several computer implementations available, closed-shell SAPT has been applied to produce numerous intermolecular potential energy surfaces for complexes of experimental interest, and to elucidate the interactions in various complexes relevant to catalysis, organic synthesis, and biochemistry. In contrast, the development of SAPT for general open-shell complexes is still a work in progress. In the last decade, new developments from several research groups, including the author's, have greatly enhanced the capabilities of SAPT. The new and emerging approaches are designed to make SAPT more widely applicable (including interactions involving multireference systems, complexes in arbitrary spin states, and intramolecular noncovalent interactions), more accurate (enhanced description of intramolecular correlation, a better account of exchange effects, relativistic SAPT, and explicitly correlated SAPT), and more efficient (enhanced density-fitted implementations, linearscaling variants, empirical dispersion, and an implementation on graphics processing units).The new developments open up avenues for SAPT applications to an unprecedented variety of weakly interacting complexes.

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“…[148][149][150] This failure can be overcome by scaling the exchange contribution 80 or by completely abandoning the S 2 approximation. 151 Overall, SAPT's lack of versatility remains perhaps its only true weakness. The "comfort zone" of the approach involves moderately sized neutral dimers and trimers.…”

Section: Applying Pt-based Edasmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

104

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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Single-determinant-based symmetry-adapted perturbation theory without single-exchange approximation

Cited by 43 publications

References 68 publications

Challenging Dogmas: Hydrogen Bond Revisited

Challenging Dogmas: Hydrogen Bond Revisited

Recent developments in symmetry‐adapted perturbation theory

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

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