Interaction in Li@Fullerenes and Li+@Fullerenes: First Principle Insights to Li-Based Endohedral Fullerenes

Abstract

This work reveals first principle results of the endohedral fullerenes made from neutral or charged single atomic lithium (Li or Li+) encapsulated in fullerenes with various cage sizes. According to the calculated binding energies, it is found that the encapsulation of a single lithium atom is energetically more favorable than that of lithium cation. Lithium, in both atomic and cationic forms, exhibits a clear tendency to depart from the center in large cages. Interaction effects dominate the whole encapsulation process of lithium to carbon cages. Further, the nature of the interaction between Li (or Li+) and carbon cages is discussed based on reduced density gradient, energy decomposition analysis, and charge transfer.

Electronic Structure Calculations on Endohedral Complexes of Fullerenes: Reminiscences and Prospects

“…In the case of [Li @C ][PF ], the measured diffraction patterns were consistent with a positional disordering of the cation within a shell with a radius of about 1.5 [Å] at 155 [K] and the presence of two crystallographically equivalent positions of Li located 1.40 ± 0.01 [Å] from the cage center at 22 [K] [ 91 ]. These experimental findings are in agreement with the original HF/DZP prediction of the radial displacement amounting to 1.30 [Å] [ 45 ] and the displacements of 1.40, 1.43, and 1.50 [Å] subsequently computed at, respectively, the M06-2X/6-31G** [ 93 ], MN15/cc-pVTZ [ 86 ], and B3LYP/cc-pVTZ [ 94 ] levels of theory.…”

Improved Estimates of Host‐Guest Interaction Energies for Endohedral Fullerenes Containing Rare Gas Atoms, Small Molecules, and Cations

“…Bai et al. studied the encapsulation of Li + in various sizes of carbon cages and found the Δ E value for Li + @C 60 , Na + @C 60 and K + @C 60 to be −33.0 kcal/mol, −25.8 kcal/mol and −29.2 kcal/mol, respectively, using the DFT(M062X)/6‐31G** method [73] . Ramachandran et al.…”

“…[72] Bai et al studied the encapsulation of Li + in various sizes of carbon cages and found the ΔE value for Li + @C 60 , Na + @C 60 and K + @C 60 to be À 33.0 kcal/mol, À 25.8 kcal/ mol and À 29.2 kcal/mol, respectively, using the DFT(M062X)/6-31G** method. [73] Ramachandran et al reported the ΔE for the Li + @C 60 complex to be À 18.8 kcal/mol at the MP2/6-31G level of theory. [34] BSSE calculations were performed using counterpoise correction scheme proposed by Boys and Bernardi.…”

External electric field to control the Diels–Alder reactions of endohedral fullerene

“…Various studies reveal that M06-2X/6-31G** level of theory works well for endohedral fullerenes. 16,18,[22][23][24] Further, to assess the suitability of this level of theory for the present work, we have performed an extensive investigation of reaction of C 60 with 1,3 cyclohexadiene and compared it with the available experimental result. 16 A barrier of B11.2 kcal mol À1 was obtained for the reaction of C 60 with 1,3 cyclohexadiene at M06-2X/6-31G** level of theory.…”