title: Interactions of aromatic radicals with water.
abstract: The interactions of the benzyl radical (1), the anilinyl radical (2), and the phenoxyl radical (3) with water are investigated using density functional theory (DFT). In addition, we report dispersion-corrected DFT-D molecular dynamics simulations on these three systems and a matrix isolation study on 1-water. The radicals 1-3 form an interesting series with the number of lone pairs increasing from none to two. The anilinyl and benzyl radicals can act as Lewis base through their unpaired electrons, the lone pairs of the heteroatoms, or the doubly occupied π orbitals of the aromatic system. Matrix isolation experiments provide evidence for the formation of a π complex between 1 and water. By combining computational and experimental techniques we identify the possible interactions between the aromatic radicals 1-3 and water, predict the structure and vibrational spectra of the resulting complexes, and analyze the effects of substitution and temperature.
authors: Department of Theory, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
authors: Rachel
authors: R
authors: Crespo-Otero
authors: Kenny
authors: K
authors: Bravo-Rodriguez
authors: Saonli
authors: S
authors: Roy
authors: Tobias
authors: T
authors: Benighaus
authors: Walter
authors: W
authors: Thiel
authors: Wolfram
authors: W
authors: Sander
authors: Elsa
authors: E
authors: Sánchez-García
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D001593:Benzyl Compounds / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D010636:Phenols / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D000814:Aniline Compounds; D001593:Benzyl Compounds; D005609:Free Radicals; D010636:Phenols; D014867:Water; C042329:phenoxy radical