Abstract
The present work starts with providing a description of the halogen bonding (XB) interaction between the halogen atom of MH3X (where M = C–Pb and X = I, At) and the N atom of HCN. This interaction leads to the formation of stable yet very weakly bound MH3X⋯NCH complexes for which the interaction energy (Eint) between MH3X and HCN is calculated using various symmetry-adapted perturbation theory (SAPT) methods combined with the def2-QZVPP basis set and midbond functions. This basis set assigns effective core potentials (ECPs) not only to the I or At atom directly participating in the XB interaction with HCN but also to the M atom when substituted with Sn or Pb. Twelve SAPT methods (or levels) are taken into consideration. According to the SAPT analysis ofEint, the XB interaction in the complexes shows mixed electrostatic-dispersion nature. Next, the accuracy of SAPTEintis evaluated by comparing with CCSD(T) reference data. This comparison reveals that high-order SAPT2+(3)method and the much less computationally demanding SAPT(DFT) method perform very well in describingEintof the complexes. However, the accuracy of these methods decreases dramatically if they are combined with the so-called Hartree-Fock correction.
Highlights
Weak intermolecular interactions play an important role in establishing the structure and stability of a broad range of chemical systems, from simple molecular complexes to macromolecular assemblies [1,2,3]
A description of the X⋅ ⋅ ⋅ N XB interaction in a series of 10 MH3X⋅ ⋅ ⋅ NCH complexes has been obtained from various symmetry-adapted perturbation theory (SAPT) methods combined with the def2-QZVPP basis set and midbond functions
This basis set assigns effective core potentials (ECPs) to the I or At atom directly participating in the XB interaction with HCN and to the M atom when substituted with Sn or Pb
Summary
Weak intermolecular interactions play an important role in establishing the structure and stability of a broad range of chemical systems, from simple molecular complexes to macromolecular assemblies [1,2,3]. The ability to describe weak intermolecular interactions accurately and efficiently differs significantly between various families of computational electronic structure methods Among these families, the symmetry-adapted perturbation theory (SAPT) [7,8,9,10,11] is capable of providing weak interaction energies accurate even up to 2–4% for benchmark systems of rare-gas dimers [9] but the computational cost of the corresponding calculations in principle scales like N7 with the system size. The symmetry-adapted perturbation theory (SAPT) [7,8,9,10,11] is capable of providing weak interaction energies accurate even up to 2–4% for benchmark systems of rare-gas dimers [9] but the computational cost of the corresponding calculations in principle scales like N7 with the system size This makes such calculations very time-consuming, especially if they are carried out for large chemical systems. These levels differ in their scaling behavior through the omission of some energy correction terms from the SAPT expansion of intermolecular interaction energy
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