Spin Density Distribution in Open-Shell Transition Metal Systems: A Comparative Post-Hartree–Fock, Density Functional Theory, and Quantum Monte Carlo Study of the CuCl2 Molecule

International audienceWe present a comparative study of the spatial distribution of the spin density (SD) of the ground state of CuCl2 using Density Functional Theory (DFT), quantum Monte Carlo (QMC), and post-Hartree-Fock wavefunction theory (WFT). A number of studies have shown that an accurate description of the electronic structure of the lowest-lying states of this molecule is particularly challenging due to the interplay between the strong dynamical correlation effects in the 3d shell of the copper atom and the delocalization of the 3d hole over the chlorine atoms. It is shown here that qualitatively different results for SD are obtained from these various quantum-chemical approaches. At the DFT level, the spin density distribution is directly related to the amount of Hartree-Fock exchange introduced in hybrid functionals and, therefore, it is not possible to draw conclusive results. At the QMC level, Fixed-node Diffusion Monte Carlo (FN-DMC) results for SD are strongly dependent on the nodal structure of the trial wavefunction employed. In the case of this open-shell system, the 3N-dimensional nodes are mainly determined by the 3-dimensional nodes of the singly occupied molecular orbital (SOMO) and FN-DMC results are found to be strongly dependent on the type of one-particle model used for generating the SOMO (here, Hartree-Fock or Kohn-Sham with a particular amount of HF exchange). Regarding wavefunction approaches, HF and CASSCF lead to strongly localized spin density on the copper atom, in sharp contrast with DFT. To get a more reliable description and shed some light on the connections between the various theoretical descriptions, Full CI-type (FCI) calculations are performed. To make them feasible for this case a perturbatively selected CI approach generating multi-determinantal expansions of reasonable size and a small tractable basis set are employed. Although semi-quantitative, these near-FCI calculations allow to clarify how the spin density distribution evolves upon inclusion of dynamic correlation effects. A plausible scenario about the nature of the SD is proposed