Toward spectroscopic accuracy for open-shell systems: molecular structure and hyperfine coupling constants of H2CN,...

In the present paper, we investigate the molecular structure and hyperfine couplings of a series of σ radicals containing first- and second-row atoms (H(2)CN,H(2)CP,NH(2),PH(2)) for which accurate gas-phase microwave results are available. The presence of α- and, especially, β-hydrogen atoms makes the evaluation of magnetic properties of these radicals particularly challenging. Geometrical parameters have been computed by the coupled-cluster ansatz in conjunction with hierarchical series of basis sets, thus accounting for extrapolation to the complete basis-set limit. Core correlation as well as higher excitations in the electronic-correlation treatment have also been taken into account. An analogous approach has been employed for evaluating hyperfine coupling constants with particular emphasis given to basis-set, correlation, and geometrical effects. The corresponding vibrational corrections, required for a meaningful comparison to experimental data, have also been investigated. The remarkable agreement with experiment confirms the reliability of the present computational approach, already validated for π radicals, thus establishing the way for setting up a benchmark database for magnetic properties.