DOI:10.1524/zpch.217.12.1565.20476

Computed EOM-CCSD ¹⁹F-¹⁹F Spin-Spin Coupling Constants in Small Organic Molecules

Two-, three-, and four-bond 19F-19F spin-spin coupling constants (nJFF) for a set of small fluoro-substituted organic molecules have been computed using ab initio equation-ofmotion coupled cluster singles and doubles (EOM-CCSD) theory. The computed values reproduce the experimental signs and magnitudes of nJFF. The straight line that relates the experimental and computed coupling constants has a slope of approximately 1 and passes through the point (0, 0Hz) within the uncertainties of the fit. Hence, EOM-CCSD values of nJFF should be excellent predictors of experimental values when these are not available. All of the components of nJFF except for the diamagnetic spin-orbit term may be large and must be evaluated if agreement between theory and experiment is to be obtained.