An integrated computational protocol for the accurate prediction of EPR and PNMR parameters of nitroxide radicals in solution.

Magnetic spectroscopic techniques such as electron paramagnetic resonance (EPR) and paramagneticNMR(PNMR) are valuabletools for understanding the structure and dynamics of complex systems such as, for example, biomolecules or nanomaterialslabeled with suitable free radicals. Unfortunately, such spectra do not give direct access to the radical structure because of thesubtle interplay between several different effects not easily separable and evaluable by experimentalists alone. In this respect,computational spectroscopy is becoming an essential and versatile tool for the assignment and interpretation of experimentalspectra. In this article, the new integrated computational approaches developed in the recent years in our research groupare reviewed. Such approaches have been applied to two widely used spin probes showing that proper account of stereoelectronic,environmental and dynamical effects leads to magnetic properties in remarkable agreement with experimentalresults.