Halogen-Bonding Interactions with π Systems: CCSD(T), MP2, and DFT Calculations

Authors

  • Dr. Alessandra Forni,

    Corresponding author
    1. Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    • Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    Search for more papers by this author
  • Dr. Stefano Pieraccini,

    Corresponding author
    1. Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    2. Dipartimento di Chimica and INSTM UdR, Università degli Studi di Milano, Via Golgi 19, 20133, Milano (Italy)
    • Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    Search for more papers by this author
  • Dr. Stefano Rendine,

    1. Dipartimento di Chimica and INSTM UdR, Università degli Studi di Milano, Via Golgi 19, 20133, Milano (Italy)
    Search for more papers by this author
  • Dr. Fabio Gabas,

    1. Dipartimento di Chimica and INSTM UdR, Università degli Studi di Milano, Via Golgi 19, 20133, Milano (Italy)
    Search for more papers by this author
  • Prof. Dr. Maurizio Sironi

    Corresponding author
    1. Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    2. Dipartimento di Chimica and INSTM UdR, Università degli Studi di Milano, Via Golgi 19, 20133, Milano (Italy)
    • Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and INSTM UdR, Via Golgi 19, 20133, Milano (Italy)
    Search for more papers by this author

Abstract

Halogen bonding is a noncovalent interaction between a halogen atom and a nucleophilic site. Interactions involving the π electrons of aromatic rings have received, up to now, little attention, despite the large number of systems in which they are present. We report binding energies of the interaction between either NCX or PhX (X=F, Cl, Br, I) and the aromatic benzene system as determined with the coupled cluster with perturbative triple excitations method [CCSD(T)] extrapolated at the complete basis set limit. Results are compared with those obtained by Møller–Plesset perturbation theory to second order (MP2) and density functional theory (DFT) calculations by using some of the most common functionals. Results show the important role of DFT in studying this interaction.

Ancillary