Analysis of the NMR through-space coupling mechanism between 19F atoms

Tell Tuttle; Jürgen Gräfenstein; Dieter Cremer

doi:10.1016/j.cplett.2004.06.084

Analysis of the NMR through-space coupling mechanism between ¹⁹F atoms

Tell Tuttle, Jürgen Gräfenstein, Dieter Cremer

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

38 Citations (Scopus)

Abstract

The through-space NMR spin-spin coupling mechanism between ¹⁹F nuclei was investigated at the coupled perturbed density functional level using a BLYP(60:40) functional and a large basis set. Through-space coupling decays exponentially with the distance R(F,F) and is strongly angular dependent. The lp(σ) and lp(σ)-lp(σ) contributions to the FC term are larger than the corresponding lp(π _ip) contributions. The passive lp(π) contributions are responsible for 10% of the FC mechanism. The PSO term is not negligible. In 1,8-difluoronaphthalene, the FC term of 56 Hz results from through-space coupling (75 Hz) and σ through-bond coupling (-19 Hz). The magnitude of through-space coupling can be predicted with a suitable model.

Original language	English
Pages (from-to)	5-13
Number of pages	9
Journal	Chemical Physics Letters
Volume	394
Issue number	1-3
Early online date	15 Jul 2004
DOIs	https://doi.org/10.1016/j.cplett.2004.06.084
Publication status	Published - 11 Aug 2004

Funding

Calculations were done on the supercomputers of the Nationellt Superdatorcentrum (NSC), Linköping, Sweden. D.C. thanks the NSC for a generous allotment of computer time. J.G. thanks Carl Tryggers Stiftelse for financial support.

Keywords

through-space coupling
NMR through-space coupling
FC term

Access to Document

10.1016/j.cplett.2004.06.084

Cite this

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title = "Analysis of the NMR through-space coupling mechanism between 19F atoms",

abstract = "The through-space NMR spin-spin coupling mechanism between 19F nuclei was investigated at the coupled perturbed density functional level using a BLYP(60:40) functional and a large basis set. Through-space coupling decays exponentially with the distance R(F,F) and is strongly angular dependent. The lp(σ) and lp(σ)-lp(σ) contributions to the FC term are larger than the corresponding lp(π ip) contributions. The passive lp(π) contributions are responsible for 10% of the FC mechanism. The PSO term is not negligible. In 1,8-difluoronaphthalene, the FC term of 56 Hz results from through-space coupling (75 Hz) and σ through-bond coupling (-19 Hz). The magnitude of through-space coupling can be predicted with a suitable model.",

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N2 - The through-space NMR spin-spin coupling mechanism between 19F nuclei was investigated at the coupled perturbed density functional level using a BLYP(60:40) functional and a large basis set. Through-space coupling decays exponentially with the distance R(F,F) and is strongly angular dependent. The lp(σ) and lp(σ)-lp(σ) contributions to the FC term are larger than the corresponding lp(π ip) contributions. The passive lp(π) contributions are responsible for 10% of the FC mechanism. The PSO term is not negligible. In 1,8-difluoronaphthalene, the FC term of 56 Hz results from through-space coupling (75 Hz) and σ through-bond coupling (-19 Hz). The magnitude of through-space coupling can be predicted with a suitable model.

AB - The through-space NMR spin-spin coupling mechanism between 19F nuclei was investigated at the coupled perturbed density functional level using a BLYP(60:40) functional and a large basis set. Through-space coupling decays exponentially with the distance R(F,F) and is strongly angular dependent. The lp(σ) and lp(σ)-lp(σ) contributions to the FC term are larger than the corresponding lp(π ip) contributions. The passive lp(π) contributions are responsible for 10% of the FC mechanism. The PSO term is not negligible. In 1,8-difluoronaphthalene, the FC term of 56 Hz results from through-space coupling (75 Hz) and σ through-bond coupling (-19 Hz). The magnitude of through-space coupling can be predicted with a suitable model.

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