A novel field of ab initio studies: complexation of simple anions within neutral cryptands
Artikel i vetenskaplig tidskrift, 2005

We present here an ab initio study on anion guest - macrocycle host relationships. The complexation of different simple inorganic anions (F - , Cl - , BF 4 - and ClO 4 - ) with the neutral cryptand, the macrotricycle (H 3 BN) 4 [(CH 2 ) n ] 6 , (n=3-6), has been studied using ab initio Hartree-Fock calculations and density functional theory using the B3LYP hybrid functional. As the side-lengths of the pure cryptands increase with the oligomeric sidechain (n), the cryptand cavity increases as n 3 . F - is the most strongly preferred anion for all cryptands, only for the largest host cavity (n=6) complexes are formed exothermally for all anion guests. Morokuma-Kitaura decomposition has been performed to analyse the total interaction energies within the created supermolecules in physically relevant terms including the importance of treatment of the basis set superposition error. According to this scheme the polarisation/charge transfer parts differ in importance amongst the complexes in facilitating a strong binding of the anion guests, but the dominant balance being that of Coulombic attraction and Pauli repulsion. © 2004 Elsevier B.V. All rights reserved.

Författare

Patrik Johansson

Chalmers, Teknisk fysik, Kondenserade materiens fysik

Erik Abrahamsson

Göteborgs universitet

Chalmers University of Technology

Per Jacobsson

Chalmers, Teknisk fysik, Kondenserade materiens fysik

Journal of Molecular Structure: THEOCHEM

0166-1280 (ISSN)

Vol. 717 215-221

Ämneskategorier

Annan teknik

DOI

10.1016/j.theochem.2004.12.021