High-Level Ab Initio Calculations of Intermolecular Interactions: Heavy Main-Group Element π-Interactions

Małgorzata Krasowska; Wolfgang B Schneider; Michael Mehring; Alexander A Auer

doi:10.1002/chem.201801758

High-Level Ab Initio Calculations of Intermolecular Interactions: Heavy Main-Group Element π-Interactions

Chemistry. 2018 Jul 17;24(40):10238-10245. doi: 10.1002/chem.201801758. Epub 2018 Jun 19.

Authors

Małgorzata Krasowska^{1

2}, Wolfgang B Schneider¹, Michael Mehring³, Alexander A Auer^{1

2}

Affiliations

¹ Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
² Present address: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 2, 45470, Mülheim an der Ruhr, Germany.
³ Technische Universität Chemnitz, Straße der Nationen 62, 09111, Chemnitz, Germany.

PMID: 29718544
DOI: 10.1002/chem.201801758

Abstract

This work reports high-level ab initio calculations and a detailed analysis on the nature of intermolecular interactions of heavy main-group element compounds and π systems. For this purpose we have chosen a set of benchmark molecules of the form MR₃ , in which M=As, Sb, or Bi, and R=CH₃ , OCH₃ , or Cl. Several methods for the description of weak intermolecular interactions are benchmarked including DFT-D, DFT-SAPT, MP2, and high-level coupled cluster methods in the DLPNO-CCSD(T) approximation. Using local energy decomposition (LED) and an analysis of the electron density, details of the nature of this interaction are unraveled. The results yield insight into the nature of dispersion and donor-acceptor interactions in this type of system, including systematic trends in the periodic table, and also provide a benchmark for dispersion interactions in heavy main-group element compounds.

Keywords: ab initio calculations; coordination chemistry; dispersion interactions; electronic structure calculations; main-group chemistry.

Abstract

Grants and funding