Biradical character in the ground state of [Mn@Si12]+: a DFT and CASPT2 study

Abstract

Both density functional theory and multi-configurational ab initio (CASPT2) calculations are used to explore the potential energy surface of the hexagonal prismatic cluster [Mn@Si₁₂]⁺. Unlike isoelectronic Cr@Si₁₂, the ground state is a biradical, with triplet and open-shell singlet states lying very close in energy. The results are discussed in the context of recent experimental studies using infra-red multiple photon dissociation spectroscopy and X-ray MCD spectroscopy.