TY - JOUR
T1 - Analysis of the NMR through-space coupling mechanism between 19F atoms
AU - Tuttle, Tell
AU - Gräfenstein, Jürgen
AU - Cremer, Dieter
PY - 2004/8/11
Y1 - 2004/8/11
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.
KW - through-space coupling
KW - NMR through-space coupling
KW - FC term
UR - http://www.scopus.com/inward/record.url?scp=3843150350&partnerID=8YFLogxK
UR - https://www.sciencedirect.com/journal/chemical-physics-letters
U2 - 10.1016/j.cplett.2004.06.084
DO - 10.1016/j.cplett.2004.06.084
M3 - Article
AN - SCOPUS:3843150350
SN - 0009-2614
VL - 394
SP - 5
EP - 13
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-3
ER -