Calculation of spin—spin coupling constants using density functional theory

Abstract A density functional method for the calculation of spin—spin coupling constants has been developed and applied to a large set of molecules. The results for the Fermi contact contribution are strongly dependent on the exchange—correlation functional. The results for proton—proton, carbon—proton and carbon—carbon coupling constants are in good agreement with experiment but the agreement worsens from N to F. Improved results for the Fermi contact contribution will require new functionals. Nevertheless, even at the current stage, the new method represents a powerful tool for the calculation of coupling constants in large organic and biological molecules.

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