title: Role of zero-point vibrational corrections to carbon hyperfine coupling constants in organic π radicals.
abstract: By analyzing a set of organic π radicals, we demonstrate that zero-point vibrational corrections give significant contributions to carbon hyperfine coupling constants, in one case even inducing a sign reversal for the coupling constant. We discuss the implications of these findings for the computational analysis of electron paramagnetic spectra based on hyperfine coupling constants evaluated at the equilibrium geometry of radicals. In particular, we note that a dynamical description that involves the nuclear motion is in many cases necessary in order to achieve a semi-quantitatively predictive theory for carbon hyperfine coupling constants. In addition, we discuss the implications of the strong dependence of the carbon hyperfine coupling constants on the zero-point vibrational corrections for the selection of exchange-correlation functionals in density functional theory studies of these constants.
authors: KTH Royal Institute of Technology, School of Biotechnology, Division of Theoretical Chemistry and Biology, S-106 91 Stockholm, Sweden.
authors: X
authors: X
authors: Chen
authors: Z
authors: Z
authors: Rinkevicius
authors: K
authors: K
authors: Ruud
authors: H
authors: H
authors: Ågren
mesh_terms: D002244:Carbon / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D009930:Organic Chemicals / Q000737:chemistry*; D011789:Quantum Theory; D014732:Vibration
chemical_list: D005609:Free Radicals; D009930:Organic Chemicals; D002244:Carbon