Berry Pseudorotation Mechanism for the Interpretation of the 19F NMR Spectrum in PF5 by Ab Initio Molecular Dynamics Simulations.

Christophe Raynaud (1) , Laurent Maron (2) , Jean-Pierre Daudey (2) , Franck Jolibois (2)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 LPCNO - Laboratoire de physique et chimie des nano-objets

For the first time, theoretical evidence that confirms the importance of the Berry pseudorotation process in the interpretation of the 19F NMR spectrum of phosphorus pentafluoride (PF5) is presented. Ab initio molecular dynamics simulations have been performed to generate a large number of configurations used for NMR parameter computations at the density functional theory level. Two different temperatures were set to highlight the effect of pseudorotation process on the NMR spectrum. Average 19F chemical shifts and spin-spin coupling constants calculated for the five fluorine atoms converge towards the NMR equivalence of the five atoms when the Berry pseudorotation mechanism is accounted for.

Domaines: Chimie théorique et/ou physique

Christophe Raynaud, Laurent Maron, Jean-Pierre Daudey, Franck Jolibois. Berry Pseudorotation Mechanism for the Interpretation of the 19F NMR Spectrum in PF5 by Ab Initio Molecular Dynamics Simulations.. ChemPhysChem, 2006, 7 (2), pp.407-413. ⟨10.1002/cphc.200500297⟩. ⟨hal-00171227⟩