Heavy atom tunnelling on XeF6pseudorotation

Itzhak Sedgi, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The uncertainty on XeF6 geometry persisted for over five decades, with elusive multiple C3v equivalent minima as an outcome of the Jahn-Teller effect. Herein we theoretically prove that XeF6 shows a genuine fluorine quantum mechanical tunnelling rearrangement, rapidly "jumping"between isomers even close to 0 K. The isoelectronic anions IF6- and TeF62- behave in the same way as XeF6, but with a lower and shorter energetical barrier they have a faster tunnelling rate. A complete isotopic analysis revealed a large k(18F)/k(19F) kinetic isotope effect. We speculate that it would be possible to experimentally observe the tunnel effect in XeF6 by means of cryogenic NMR or IR.

Original languageEnglish
Pages (from-to)17725-17730
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume22
Issue number31
DOIs
StatePublished - 21 Aug 2020

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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