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Approximating correlation effects in multiconfigurational self-consistent field calculations of spin-spin coupling constants

San Fabián, J.; Díez, E.; García de la Vega, J.M.; Suardíaz, R.

Journal of Chemical Physics 128(8): 084108

2008

The multiconfigurational self-consistent field (MCSCF) method in their approximations restricted and complete active spaces (RAS and CAS) provides a theoretically accurate description of the coupling constants of a wide range of molecules. To obtain accurate results, however, very large basis sets and large configuration spaces must be used. Nuclear magnetic resonance coupling constants for the equilibrium geometry have been calculated for a series of small molecules using approximated correlation contributions. The four contributions to the coupling constants (Fermi contact, spin dipolar, orbital paramagnetic, and orbital diamagnetic) have been calculated at the CAS and RAS MCSCF and second-order polarization propagator approximation levels using a large basis set. An additive model that considers the effect on the coupling constants from excitation of more than two electrons and from core-electron correlation is used to estimate the coupling constants. Compared with the experimental couplings, the best calculated values, which correspond to the MCSCF results, present a mean absolute error of 3.6 Hz and a maximum absolute deviation of 13.4 Hz. A detailed analysis of the different contributions and of the effects of the additive contributions on the coupling constants is carried out.

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