Unexpected Geometrical Effects on Paramagnetic Spin-Orbit and Spin-Dipolar (2)J(FF) Couplings

作者：Ducati Lucas C; Contreras Ruben H; Tormena Claudio F^*

来源：Journal of Physical Chemistry A, 2012, 116(20): 4930-4933.

DOI：10.1021/jp301912x

The second-rank tensor character of the paramagnetic spin orbit and spin dipolar contributions to nuclear spin spin coupling constants is usually ignored when NMR measurements are carried out in the isotropic phase. However, in this study it is shown that isotropic (2)J(FF) couplings strongly depend on the relative orientation of the C F bonds containing the coupling nuclei and the eigenvectors of such tensors. Predictions about such effect are obtained using a qualitative approach based on the polarization propagator formalism at the RPA, and results are corroborated performing high-level ab initio spin spin coupling calculations at the SOPPA(CCSD)/EPR-III//MP2/EPR-III level in a model system. It is highlighted that no calculations at the RPA level were carried out in this work. The quite promising results reported in this paper suggest that similar properties are expected to hold for the second-rank nuclear magnetic shielding tensor.

• 出版日期2012-5-24