DFT study of nitroxide radicals: explicit modeling of solvent effects on the structural and electronic characteristics of 4-amino-2,2,6,6-tetramethyl-piperidine-N-oxyl.

An explicit DFT modeling of water surroundings on the electron paramagnetic resonance properties of 4-amino-2,2,6,6-tetramethyl-piperidine-N-oxyl (TA) has been performed. A stepwise hydration of TA is accompanied with certain changes in geometrical parameters (bond lengths and angles) and redistribution of partial electric charges in TA. An aqueous cluster of 45 water molecules can be considered as an appropriate model for a complete aqueous shell around TA, although most of the structural and electronic characteristics of TA already converge at about 10 water molecules. Water surroundings induce an increase in electron spin density on the nitrogen atom of the nitroxide fragment due to stabilization of the polar resonance structure > N+•O− at the expense of less polar structure > NO•. The water-induced rise of the isotropic splitting constant aiso, calculated from the contact term of the hyperfine interaction, comprises Δaiso(ρN2) = 2.2–2.5 G, which is typical of experimental value for TA. There are two contributions to the solvent effect on the aiso(ρN2) value: the redistribution of spin density in the nitroxide fragment (polarity effect) and water-induced distortions of TA geometry. Microscopic variations in a hydrogen-bonded water network cause noticeable fluctuations of the splitting constant aiso(ρN2). Calculations of the atomic spin density (σN2) allowed us to compute the splitting constant from the relationship aiso(σN2) = QσN2, where Q = 36.2 G. A practical advantage of using this relationship is that it gives ‘smoothed’ values of the splitting constant, which are sensitive to the environment polarity but remain tolerant to microscopic fluctuations of the hydrogen-bonded water network around a spin-label molecule. Copyright © 2010 John Wiley & Sons, Ltd.