title: Weak interactions in ion–ligand complexes of C3H3(+) isomers: competition between H-bound and C-bound structures in c-C3H3(+)·L and H2CCCH(+)·L (L = Ne, Ar, N2, CO2, and O2).
abstract: Explicitly correlated coupled cluster theory at the CCSD(T)-F12x level (T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys.127, 221106, 2007) has been employed to study structures and vibrations of complexes of type c-C(3)H(3)(+)·L and H(2)C(3)H(+)·L (L = Ne, Ar, N(2), CO(2), and O(2)). Both cations have different binding sites, allowing for the formation of weak to moderately strong hydrogen bonds as well as "C-bound" or "π-bound" structures. In contrast to previous expectations, the energetically most favourable structures of all H(2)C(3)H(+)·L complexes investigated are "C-bound", with the ligand bound to the methylenic carbon atom. The theoretical predictions enable a more detailed interpretation of infrared photodissociation (IRPD) spectra than was possible hitherto. In particular, the bands observed in the range 3238-3245 cm(-1) (D. Roth and O. Dopfer, Phys. Chem. Chem. Phys.4, 4855, 2002) are assigned to essentially free acetylenic CH stretching vibrations of the propargyl cation in "C-bound" H(2)C(3)H(+)·L complexes.
authors.affiliation: Institut für Physikalische Chemie, Universität Göttingen, Tammannstraße 6, 37077 Göttingen, Germany. pbotsch@gwdg.de
authors.forename: Peter
authors.initials: P
authors.lastname: Botschwina
authors.forename: Rainer
authors.initials: R
authors.lastname: Oswald
authors.forename: Otto
authors.initials: O
authors.lastname: Dopfer