Biradical character in the ground state of [Mn@Si12]+: a DFT and CASPT2 study. Issue 34 (15th August 2016)

• Record Type: Journal Article
• Authors: Arcisauskaite, Vaida; Fijan, Domagoj; Spivak, Mariano; Graaf, Coen de; McGrady, John E.
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 34(2016)
• Page Start: 24006
• Page End: 24014
• Publication Date: 2016-08-15
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp03534e
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : DFT and CASPT2 calculations reveal that the ground state of [Mn@Si12 ] + is a biradical, quite unlike isoelectronic and isostructural Cr@Si12 . 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.