Accurate, precise, and efficient theoretical methods to calculate anion-π interaction energies in model structures

Pál D. Mezei, G. Csonka, Adrienn Ruzsinszky, Jianwei Sun

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

A correct description of the anion-π interaction is essential for the design of selective anion receptors and channels and important for advances in the fi eld of supramolecular chemistry. However, it is challenging to do accurate, precise, and efficient calculations of this interaction, which are lacking in the literature. In this article, by testing sets of 20 binary anion-π complexes of fluoride, chloride, bromide, nitrate, or carbonate ions with hexafluorobenzene, 1,3,5-tri fluorobenzene, 2,4,6-trifluoro-1,3,5-triazine, or 1,3,5-triazine and 30 ternary π-anion-π′ sandwich complexes composed from the same monomers, we suggest domain-based local-pair natural orbital coupled cluster energies extrapolated to the complete basis-set limit as reference values. We give a detailed explanation of the origin of anion-π interactions, using the permanent quadrupole moments, static dipole polarizabilities, and electrostatic potential maps. We use symmetry-adapted perturbation theory (SAPT) to calculate the components of the anion-π interaction energies. We examine the performance of the direct random phase approximation (dRPA), the second-order screened exchange (SOSEX), local-pair natural-orbital (LPNO) coupled electron pair approximation (CEPA), and several dispersion-corrected density functionals (including generalized gradient approximation (GGA), meta-GGA, and double hybrid density functional). The LPNO-CEPA/1 results show the best agreement with the reference results. The dRPA method is only slightly less accurate and precise than the LPNO-CEPA/1, but it is considerably more efficient (6-17 times faster) for the binary complexes studied in this paper. For 30 ternary π-anion-π′ sandwich complexes, we give dRPA interaction energies as reference values. The double hybrid functionals are much more e fficient but less accurate and precise than dRPA. The dispersion-corrected double hybrid PWPB95-D3(BJ) and B2PLYP-D3(BJ) functionals perform better than the GGA and meta-GGA functionals for the present test set. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)360-371
Number of pages12
JournalJournal of Chemical Theory and Computation
Volume11
Issue number1
DOIs
Publication statusPublished - Jan 13 2015

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Model structures
Anions
Negative ions
anions
approximation
interactions
Triazines
functionals
energy
Electrons
Fluorobenzenes
orbitals
gradients
Supramolecular chemistry
Carbonates
Bromides
Fluorides
Nitrates
Chlorides
Electrostatics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Accurate, precise, and efficient theoretical methods to calculate anion-π interaction energies in model structures. / Mezei, Pál D.; Csonka, G.; Ruzsinszky, Adrienn; Sun, Jianwei.

In: Journal of Chemical Theory and Computation, Vol. 11, No. 1, 13.01.2015, p. 360-371.

Research output: Contribution to journalArticle

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