Accurate Prediction of Hyperfine Coupling Tensors for Main Group Elements Using a Unitary Group Based Rigorously...

We present the development of a perturbative triples correction scheme for the previously reported unitary group based spin-adapted combinatoric open-shell coupled-cluster (CC) singles and doubles (COS-CCSD) approach and report on the applications of the newly developed method, termed "COS-CCSD(T)", to the calculation of hyperfine coupling (HFC) tensors for radicals consisting of hydrogen, second- and third-row elements. The COS-CCSD(T) method involves a single noniterative step with [Formula: see text] scaling of the computational cost for the calculation of triples corrections to the energy. The key feature of this development is the use of spatial semicanonical orbitals generated from standard restricted open-shell Hartree-Fock (ROHF) orbitals, which allows the unperturbed Hamiltonian operator to be defined in terms of a diagonal spin-free Fock operator. The HFC tensors are computed as a first-order property via implementation of an analytic derivative scheme. The required one-particle spin density matrix is computed by using one- and two-particle spin-free density matrices that are obtained from the analytic derivative implementation, in this way avoiding the use of any spin-dependent operator and maintaining spin adaptation of the CC wavefunction. Benchmark calculations of HFC tensors for a set of 21 radicals indicate reasonably good agreement of the COS-CCSD(T) results with experiment and a consistent improvement over the COS-CCSD method. We demonstrate that the accuracies of the isotropic hyperfine coupling constants obtained in unrestricted HF (UHF) reference based spin-orbital CCSD(T) calculations deteriorate when spin contamination in the UHF wavefunction is large, and the results may even become qualitatively incorrect when spin polarization is the driving mechanism. Within a similar noniterative perturbative treatment of triple excitations, the spin-adapted COS-CCSD(T) approach produces accurate results, thus ensuring cost-effectiveness together with reliability.