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Berry Pseudorotation Mechanism for the Interpretation of the 19 F NMR Spectrum in PF 5 by Ab Initio Molecular Dynamics Simulations
Author(s) -
Raynaud Christophe,
Maron Laurent,
Daudey JeanPierre,
Jolibois Franck
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500297
Subject(s) - pseudorotation , chemistry , computational chemistry , ab initio , density functional theory , coupling constant , nmr spectra database , chemical shift , nuclear magnetic resonance spectroscopy , molecular dynamics , molecule , chemical physics , stereochemistry , spectral line , physics , organic chemistry , quantum mechanics
10.1002/cphc.200500297.abs For the first time, theoretical evidence that confirms the importance of the Berry pseudorotation process in the interpretation of the 19 F NMR spectrum of phosphorus pentafluoride (PF 5 ) 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 19 F 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.