Role of zero-point vibrational corrections to carbon hyperfine coupling constants in organic pi radicals

• By analyzing a set of organic pi 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.

Ämnesord

NATURVETENSKAP  -- Fysik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences (hsv//eng)

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Nyckelord

Density-Functional Theory

Electron-Spin-Resonance

Restricted-Unrestricted Approach

Ribonucleotide Reductase

Paramagnetic-Resonance

Polyatomic-Molecules

Tryptophan Radicals

Magnetic-Properties

Anion-Radicals

Esr Spectra

Publikations- och innehållstyp

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