title: Theoretical investigation of the EPR hyperfine coupling constants in amino derivatives.
abstract: The HFCCs of the radical cations of a series of amines have been determined at different levels of approximation including the CISD, QCISD, and CCSD ab initio correlated methods and density functional theory approaches employing the B3LYP, PBE0, BHandHLYP, TPSS, and BLYP exchange-correlation functionals. Although quantitative differences with respect to experimental data have been noticed, these are mostly systematic within a given class of N and H atoms. As a consequence, these different levels of theory are reliable in most cases to account for the substituent and structure effects on the HFCCs of amines. Linear regression fits have then been performed to reach quantitative agreement between the theoretical and experimental values. This has finally been substantiated by considering the EPR signal of the recently synthesized radical cations of two derivatives of [10-(4-aminophenyl)-9-anthryl]aniline as well as in confirming a recent assignment of the EPR signal of n-propylamine.
authors.affiliation: Laboratory of Intermolecular Interactions, Faculty of Chemistry, University of Warsaw, 02-093, Warsaw, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Rogowska
authors.forename: Sébastien
authors.initials: S
authors.lastname: Kuhl
authors.forename: Raphaël
authors.initials: R
authors.lastname: Schneider
authors.forename: Alain
authors.initials: A
authors.lastname: Walcarius
authors.forename: Benoît
authors.initials: B
authors.lastname: Champagne
mesh_terms: D000588:Amines / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*
chemical_list: D000588:Amines