Does DFT-SAPT method provide spectroscopic accuracy?

Shirkov, Leonid; Makarewicz, Jan

doi:10.1063/1.4907204

Cited by 12 publications

(8 citation statements)

References 162 publications

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“…In the more general case, SAPT(DFT) calculations employing an ab initio derived potential, computed from Brueckner doubles densities using the Zhao‐Morrison‐Parr (ZMP) method, and the ALDA exchange correlation kernel have been investigated by Boese and Jansen . The resulting SAPT(ZMP) approach showed an overall improved performance over SAPT(DFT), in particular, essentially removing the overbinding of the latter in the case of rare gas dimers …”

Section: Enhancing the Accuracy Of Saptmentioning

confidence: 99%

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Recent developments in symmetry‐adapted perturbation theory

Patkowski

2019

WIREs Comput Mol Sci

159

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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Section: Enhancing the Accuracy Of Saptmentioning

confidence: 99%

“…359 The resulting SAPT(ZMP) approach showed an overall improved performance over SAPT(DFT), in particular, essentially removing the overbinding of the latter in the case of rare gas dimers. 360…”

Section: Improved Expressions For Exchange Energiesmentioning

confidence: 99%

Recent developments in symmetry‐adapted perturbation theory

Patkowski

2019

WIREs Comput Mol Sci

159

144

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“…[51] Ar ecent major blind benchmarking exercise [52] came to the conclusion "Thus, one may say that SAPT(DFT) gives results of CCSD(T) qualitya tD FT costs for dimers with up to af ew dozens of atoms. "D oubts have been expressed [53] as to whether DFT-SAPT can provide spectroscopic accuracy for rareg as dimers but this study used standardh ybrid XC potentials. Earlier work using "exact" exchange-correlation potentials for the monomers in the helium dimer showedt hat DFT-SAPT gives essentially perfecta greement with benchmark Quantum Monte-Carlo calculations.…”

Section: Calculated Bindinge Nergiesmentioning

confidence: 99%

Trifluoromethyl: An Amphiphilic Noncovalent Bonding Partner

2017

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The traditional picture of bonded fluorine as strongly δ-suggests that it can only interact with electrophilic centers [1] and does not form halogen bonds,[2] however this view does not take polarization into account. In trifluoromethyl groups negative hyperconjugation (anomeric polarizability) results in two of the fluorine atoms becoming more polarizable and thus more able to form σ-holes.[3] The unique combination of the anomeric effect and the group-polarization process associated with it in trifluoromethyl groups allows the most negative molecular electrostatic potential (MEP) on the surface in contact with a nucleophile to become zero, so that the area of positive MEP on the backside of the carbon atom becomes dominant. The unusual group polarizability therefore results in the trifluoromethyl groups exhibiting amphiphilic behavior, i.e. acting not only as nucleophiles (as expected) but also as electrophiles and thus as halogen bond donors. A survey of experimental crystal structures obtained from the Cambridge Structural Database (CSD) and the Protein Databank (PDB) as well as MP2/aug-cc-pVDZ calculations on model systems demonstrate these interactions. In particular, a survey of structures in the CSD containing the trifluorotoluene moiety shows that the trifluoromethyl group forms more, and stronger, interactions with neighboring species than the F in fluorobenzene moieties, which does not experience anomeric polarization.

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“…22 While interaction energies obtained with them are very useful for vibrational-rotational tunneling spectroscopy of van der Waals complexes, 39,40 they can certainly not be considered as spectroscopically accurate. 41,42 On the other hand, since Kohn-Sham DFT establishes an invertible connection between the xc potential and the electron density, the density can be used to construct the xc potential. [43][44][45][46] In the two-electron case, an exact Hylleraas density can be inverted to yield an essentially exact xc potential, a possibility which has been exploited for SAPT calculations of the Helium dimer.…”

Section: Introductionmentioning

confidence: 99%

ZMP-SAPT: DFT-SAPT using ab initio densities

Boese

Jansen

2019

The Journal of Chemical Physics

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Symmetry Adapted Perturbation Theory (SAPT) has become an important tool when predicting and analyzing intermolecular interactions. Unfortunately, DFT-SAPT, which uses Density Functional Theory (DFT) for the underlying monomers, has some arbitrariness concerning the exchange-correlation potential and the exchange-correlation kernel involved. By using ab initio Brueckner Doubles densities and constructing Kohn-Sham orbitals via the Zhao-Morrison-Parr (ZMP) method, we are able to lift the dependence of DFT-SAPT on DFT exchange-correlation potential models in first order. This way, we can compute the monomers at the Coupled-Cluster level of theory and utilize SAPT for the intermolecular interaction energy. The resulting ZMP-SAPT approach is tested for small dimer systems involving rare gas atoms, cations, and anions and shown to compare well with the Tang-Toennies model and coupled cluster results.

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Does DFT-SAPT method provide spectroscopic accuracy?

Cited by 12 publications

References 162 publications

Recent developments in symmetry‐adapted perturbation theory

Recent developments in symmetry‐adapted perturbation theory

Trifluoromethyl: An Amphiphilic Noncovalent Bonding Partner

ZMP-SAPT: DFT-SAPT using ab initio densities

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