The magnetic coupling in manganese-based dinuclear superhalogens and their analogues. A theoretical characterization from a combined DFT and BS study

Abstract

The structures, relative stabilities, vertical detachment energies and magnetic coupling properties of a series of manganese-based dinuclear superhalogens and their isoelectronic analogues are explored via a combined density functional theory and broken symmetry study. Both the capabilities of various exchange-correlation functionals and basis set effects are investigated. The large magnitudes of the calculated exchange coupling constants indicate clearly the apparent molecular magnetism of these new types of superhalogen. Encouragingly, the high possibility of the coexistence of both high stability and strong magnetic coupling in these new polynuclear superhalogens is also confirmed. Besides these, the larger magnitudes of the calculated coupling constants of iron-based clusters here, compared with the homodinuclear [Mn(2)Cl(5)](-) cluster, demonstrate the possibility of the existence of strong magnetic coupling in potential iron-based homo- and heterodinuclear superhalogens. The analysis of spin density distribution is also performed in order to understand the coupling mechanisms.

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study

“…2,3 Polynuclear superhalogens, of which the number of central atoms is larger than one, 2, 3 possess the advantage of increasing the number of ligands while maintaining their high stability 2 and thus they have attracted more and more attention from both experimental and theoretical studies, respectively. 8 recent researches have pointed out another interesting property of polynuclear superhalogens, the existence of remarkable molecular magnetism 13,18,[21][22][23]25 because of the partially filled 3d shell of transition metal (TM) central atoms. Therefore, novel magnetic materials are clearly a brand-new research direction of superhalogens.…”

“…Encouragingly, positive progress in this direction has already been achieved because the coexistence of high stability and strong magnetic coupling has been verified by our recent work of combined density functional theory 26 and broken-symmetry [27][28][29][30][31][32][33][34][35][36] (DFT-BS) study of dinuclear TM-based superhalogens. 22 In pursuit of further advance in this direction, a series of 18 TM-based trinuclear superhalogen anions [M 3 X 7 ] − (M = Mn II , Tc II , and X = F − , Cl − , Br − ) is investigated in this work. Although some of them have been reported in previous work, 13 a detailed theoretical study focusing on the magnetic properties of trinuclear superhalogens is still scarce according to our best knowledge.…”

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

“…5,[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] Along with the deepening of the related researches, it has been a Author to whom correspondence should be addressed. Electronic mail: rayinyin@nwu.edu.…”

Theoretical Search for an Iron‐Based Magnetic Superhalogen with Halogen or Interhalogen as Ligand

“…The Mn x Cl 2x+1 species can be magnetic, thus they have the potential to serve as building blocks of a new class of salts with magnetic and superoxidizing properties. Following this discovery, Yin et al [41] theoretically studied the magnetic coupling of . Furthermore, the iron also exhibits multiple oxidation states.…”