Localization‐vs‐Delocalization of 5f Orbitals in Superatom Systems. Issue 3 (13th February 2018)

• Record Type: Journal Article
• Authors: Gao, Yang; Jiang, Wanrun; Xu, Dexuan; Wang, Zhigang
• Is Part Of: Advanced theory and simulations. Volume 1:Issue 3(2018)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-02-13
• Subjects: 5f electrons -- ds electrons -- dual nature -- first principles -- superatoms; Science -- Simulation methods -- Periodicals; Science -- Methodology -- Periodicals; Engineering -- Simulation methods -- Periodicals; Engineering -- Methodology -- Periodicals; 507.21
• DOI: 10.1002/adts.201700038
• Languages: English
• ISSNs: 2513-0390

Abstract

Abstract: A long‐standing debate on the system containing the actinide element is the extent of localization and participation of the 5f orbitals in chemical bonding across the actinide series. Here, we illuminate that the 5f orbitals have both dual nature in superatomic bonding for protactinium, uranium, neptunium, and plutonium using density functional theory. Electronic structure analysis reveals that the partial 5f electrons are active and could be preferentially excited to 6d shells to satisfy jelliumic bonding of the 18‐electron rule (1S 2 1P 6 1D 10 ). In contrast, the extra 5f electrons are more localized for neptunium and plutonium compared with protactinium and uranium, and present antiferromagnetic and ferromagnetic couplings for the spin arrangements between actinide atoms and confined gold clusters, and largely localized at the actinide atom. This work offers not only a new recipe for breeding magnetic superatoms, but also is very promising for the designing of superconducting materials and heavy‐fermion systems. Abstract : In superatomic systems of light actinides, the 5f orbitals have both localization, which could adjust magnetic coupling, and delocalization, satisfying jelliumic bonding of the 18‐electron rule.