Explanation of the different preferential binding sites for Ce and La in M2@C80 (M = Ce, La)—a density functional theory prediction

Computational Termochemistry Study of the C80 Isomers and Their Endo Lanthanum Complexes by Applying Homodesmotic and Isodesmic Reactions

“…Furthermore in almost all cases, the space between lanthanum and the nearest neighboring carbon atom is found to measure between 2.5 and 2.6 Å; values which fall within the interval of the normal bond between La and C [39]. Thus it would seem that lanthanum ions are fixed to the inner wall on the basis of our calculation, this situation has been reported early in experimental as well as theoretical work [40,41] and some interesting recent works have mentioned some similar behavior for several endohedral complexes [42,43], indeed the original idea of strong repulsion between both lanthanum positive ions [44] has changed because it has been demonstrated [41] that the transfer of electrons from lanthanum to the cage can be partial, therefore it is possible to have some amount of covalent bond between the lanthanum atoms. The indications of motion among the lanthanum particles within the cages cited above were considered in studies where Sc or Ce are the species involved.…”

Molecular geometries, electronic properties, and vibrational spectroscopic studies of endohedral metallofullerenes TM@C24 and TM@C24H12 (TM = Cr, Mo, and W)

“…Moreover, these properties have also made them prominent species in nanotechnology [2][3][4] and bio-medicine [5][6][7]. Now there have been some previous theoretical and experimental studies on endohedral complexes doped with one metal atom [8][9][10][11][12][13][14][15][16][17][18][19][20].…”

Modification of the conductance of single fullerene molecules by endohedral doping

“…16͒ using the PBE functional and basis sets and effective core potentials ͑ECPs͒ as in previous studies of endohedrally doped fullerenes on noble metal surfaces, 17 with good quality basis set and ECP for Ce as in Ref. 18. The calculated adsorption geometry of Ce 2 @C 80 on Cu͑111͒ is shown in Fig.…”

“…Both HOMO and LUMO are localized on the encapsulated Ce atoms. 18 Upon adsorption on Cu͑111͒, the low lying unoccupied states are dominated by Ce and Cu contributions with surprisingly low cage contributions ͑carbon content Ͻ8%͒ ͓Fig. 3͑b͔͒.…”