Basis sets and active space in multiconfigurational self-consistent field calculations of nuclear magnetic resonance spin–spin coupling constants

Abstract

The dependence of spin–spin nuclear magnetic resonance (NMR) coupling constants on the basis set and electron correlation has been investigated in methane using Hartree–Fock and multiconfigurational self-consistent field wave functions (HF-SCF and MCSCF). The effect of the size, contraction, and tight s functions of the basis sets is analyzed. Some suggestions about the contraction scheme are indicated. MCSCF wave functions with different numbers of active orbitals and different numbers of excited electrons were used. An approximation to determine spin–spin coupling constants at a high level of electron correlation from three calculations with a smaller level of correlation and reduced computational cost is investigated. The best calculated JCH1 and JHH2 couplings are 120.63 and −13.23 Hz, respectively, which are 0.24 and 1.24 Hz smaller than those experimentally obtained for the equilibrium geometry. The remaining error in these coupling constants can be attributed mainly to correlation and not to basis set effects.