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

doi:10.1021/jp8100078

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 journal › Article › peer-review

Abstract / Description of output

The enormous temperature dependence of the ²J_PP 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 C_s and C_2v symmetry, exist for the S and Se compounds. The C_s and C_2v conformers have very different ²J_PP 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 language	English
Pages (from-to)	938-942
Number of pages	5
Journal	The Journal of Physical Chemistry A
Volume	113
DOIs	https://doi.org/10.1021/jp8100078
Publication status	Published - 5 Feb 2009

Keywords / Materials (for Non-textual outputs)

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

Access to Document

10.1021/jp8100078

Cite this

@article{68d23274ec564d0697599d4696b6b6bd,

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

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.",

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

author = "Reilly, {Anthony M.} and Wann, {Derek A.} and Rankin, {David W. H.}",

year = "2009",

month = feb,

day = "5",

doi = "10.1021/jp8100078",

language = "English",

volume = "113",

pages = "938--942",

journal = "The Journal of Physical Chemistry A",