What makes the huge 31P-31P Coupling Constants in S(PF2)2 and Se(PF2)2 vary so much with temperature?

Anthony M. Reilly, Derek A. Wann, David W. H. Rankin

Research output: Contribution to journalArticlepeer-review

Abstract

The enormous temperature dependence of the 2JPP coupling constants in S(PF2)2 and Se(PF2)2 has been explained by a theoretical investigation of their conformations and NMR coupling constants. In contrast, the coupling in O(PF2)2 is almost invariant. Gas electron diffraction data for S(PF2)2 have been reinterpreted. The results show that two conformers, with Cs and C2v symmetry, exist for the S and Se compounds. The Cs and C2v conformers have very different 2JPP coupling constants (-12.6 and 395.2 Hz for S(PF2)2 at B3LYP/aug-cc-pVQZ) and thermal interconversion of these conformers explains the experimental behavior.

Original languageEnglish
Pages (from-to)938-942
Number of pages5
JournalThe Journal of Physical Chemistry A
Volume113
DOIs
Publication statusPublished - 5 Feb 2009

Keywords

  • GENERALIZED GRADIENT APPROXIMATION
  • CORRELATED MOLECULAR CALCULATIONS
  • PHASE ELECTRON-DIFFRACTION
  • DENSITY-FUNCTIONAL THEORY
  • GAUSSIAN-BASIS SETS
  • AB-INITIO
  • ATOMS
  • EXCHANGE
  • THERMOCHEMISTRY
  • ENERGIES

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