Theoretical DFT Study of Atomic Structure and Spin States of the Co_x(C₆₀)_n (x = 3−8, n = 1,2) Complex Nanoclusters

Abstract

Atomic structure and spin states of a set of Co x and Co x (C60) n (x = 3−8, n = 1, 2) clusters are studied using a sophisticated ab initio GGA calculations. It is shown that high-spin low-symmetry structure of free-standing Co x clusters is determined by Jahn−Teller distortions. Formation of η 2 , η 2 ′ or η 1 coordination bonds between Co x fragment and C60 molecules through carbon hexagons results in stable complex nanoclusters with nonmonotonic change of average spin momentum upon the number of cobalt atoms in the Co x cores. The theoretical results are compared with corresponding experimental data.

Large orbital magnetic moments of small, free cobalt cluster ions Co${_n^+}$ with n ${ \leqslant 9}$

“…For the smaller Co 4 , 5 clusters, the comparison to the predictions for neutrals, not shown in figure 4, shows that almost all studies predict ground state spin multiplicities for the neutral species which are higher than the ones determined in this work, and also higher than predicted, [23,27,28,29] for the cationic species. [13,30,31,32,33,34,35,36,37,38,29,39,40,41,42] Contrastingly, for t he larger neutral Co 6 -9 clusters, the majority [32,33,34,35,36,37,38,29,40,41] of the studies predict lower spin multiplicities for the neutral species t han t he ones determined here for t he cationic one::;, and even lower t han predicted for cat ion::;, [23,28,29,24] while only two studies [13,30] predict higher spin multiplicities. For the orbital magnetic moment of Co;i with 4 ~ n ~ 9 there are no predictions available in the literature.…”

“…The lines are guides to the eye. figure 4, shows that almost all studies predict ground state spin multiplicities for the neutral species which are higher than the ones determined in this work, and also higher than predicted [23,[27][28][29], for the cationic species [13,[29][30][31][32][33][34][35][36][37][38][39][40][41][42]. Contrastingly, for the larger neutral Co 6-9 clusters, the majority [29, 32-38, 40, 41] of the studies predict lower spin multiplicities for the neu tral species than the ones determined here for the cationic ones, and even lower than predicted for cations [23,24,28,29], while only two studies [13,30] predict higher spin multiplicities.…”

Coordination chemistry on carbon surfaces

“…The results indicate that the 2 coordination is energetically preferable for all systems. Next, DFT calculations were performed on higher systems Co n (C 60 ) m (n = 3-8 and m = 1, 2) [513]. The coordination of Co clusters to one fullerene dramatically changes the structure of the cluster cores.…”

Theoretical DFT Investigation of Structure and Electronic Properties of η5-Cyclopentadienyl Half-Sandwich Organochalcogenide Complexes

“…The study of organometallic compounds is a central area of research in inorganic and organic chemistry for many years, with a particular focus on half-sandwich species [1][2][3][4]. They are characterized by a metal ion coordinated by two organic ligands and have proven to be of great interest in recent decades due to their potential applications in the fields of catalysis, materials science, and electronics [5][6][7][8]. Among the different types, those containing η 5 -cyclopentadienyl (Cp) ligands have garnered significant attention, as Cp is known to form stable complexes with transition metals and is a common feature in many industrially relevant catalysts and materials [9][10][11][12].…”