Tuning of NMR and EPR parameters by vibrational averaging and environmental effects: an integrated computational approach

Abstract

Reliable computations of NMR and EPR spectroscopic parameters for flexible molecules in condensed phases require a proper account of stereo-electronic, dynamic, and environmental effects. In the framework of density functional theory methods, these effects can be introduced by second-order vibrational perturbation theory and polarisable continuum models. Two test studies illustrate potentialities of the integrated computational approach we have developed in the last years for these purposes. Further extensions to mixed discrete-continuum models and stochastic approaches for long-time dynamical effects are also sketched.

Keywords:

• NMR spectroscopy
• EPR spectroscopy
• computational spectroscopy
• solvent effects
• vibrational averaging

Acknowledgements

The authors gratefully acknowledge support from COST (Action CoDECS: ‘COnvergent Distributed Environment for Computational Spectroscopy’), and Chiara Cappelli would also like to acknowledge support from the Italian MIUR PRIN 2009 (Sviluppo di modelli accurati e di codici veloci per il calcolo di spettri vibrazionali) and FIRB 2010 (Futuro in Ricerca Protocollo RBFR10Y5VW).