Computational tools for the interpretation of electron spin resonance spectra in solution

Abstract

Spectroscopic observables can be used for monitoring relaxation processes of molecules. In particular, electron spin resonance of stable multi-radicals is sensitive to the details of the rotational and internal dynamics in rigid and flexible molecules. Integration with advanced theoretical/computational methods proves to be particularly effective to acquire direct information on long-range relaxation processes, based on molecular dynamics, multi-scale approaches and coarse-graining treatments. Together, experimental data and computational interpretation provide a way to understand the effect of chemical changes on specific systems. In this paper we review computational tools aimed at the characterisation of dynamical properties of molecules gathered from electron spin resonance measurements. Stochastic models are employed, based on a number of structural parameters that are calculated at atomistic and/or mesoscopic level depending on their nature. Open source software tools built as user-friendly ‘virtual spectroscopes’ targeted for use by experimentalists are provided as a kind of extension of the laboratory equipment. An overview of their range of applicability is provided.

Keywords:

• electron spin resonance
• integrated computational approach
• stochastic modelling
• density functional theory
• molecular dynamics

Acknowledgements

This work was partially supported by the Italian Ministero dell'Istruzione, Università e Ricerca, COST-CMTS Action CM1002 (CODECS), and Fondazione Cariparo (Project M3PC).