title: Molecular aniline clusters. I. The electronic ground state.
abstract: The aniline dimer and trimer are investigated in their electronic ground state. The potential energy surface was thoroughly searched for low lying minima by applying global optimizations on a model potential, which is recalibrated on-the-fly by ab initio calculations (spin-component-scaled LMP2) at relevant configurations. The most stable structure of the dimer corresponds to a head-to-tail arrangement with both aniline monomers being nearly equivalent. DFT-SAPT calculations reveal that the interaction energy is dominated by van der Waals dispersion, which is of comparable size as for the benzene dimer, but with a much larger total interaction energy than for the latter. The global minimum of the aniline trimer corresponds to a hydrogen bonding arrangement involving three directional NH-N hydrogen bonds, with the individual monomers being clearly distinguishable. Nonadditive three-body dispersion contributions appear to play a minor role for the trimer.
authors.affiliation: Institute of Physical and Theoretical Chemistry, University of Regensburg, Universitätsstrasse 31, Regensburg D-93040, Germany.
authors.forename: Dominik
authors.initials: D
authors.lastname: Schemmel
authors.forename: Martin
authors.initials: M
authors.lastname: Schütz
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D019281:Dimerization; D004583:Electrons; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000814:Aniline Compounds; C023650:aniline